Cobalt Single-Atom Reverse Hydrogen Spillover for Efficient Electrochemical Water Dissociation and Dechlorination.

Efficient water dissociation to atomic hydrogen (H*) with restrained recombination of H* is crucial for improving the H* utilization for electrochemical dechlorination, but is currently limited by the lack of feasible electrodes. Herein, we developed a monolithic single-atom electrode with Co single atoms anchored on the inherent oxide layer of titanium foam (Co1-TiOx/Ti), which can efficiently dissociate water into H* and simultaneously inhibit the recombination of H*, by taking advantage of the single-atom reverse hydrogen spillover effect. Experimental and theoretical calculations demonstrated that H* could be rapidly generated on the oxide layer of titanium foam, and then overflowed to the adjacent Co single atom for the reductive dechlorination. Using chloramphenicol as a proof-of-concept verification, the resulting Co1-TiOx/Ti monolithic electrode exhibited an unprecedented performance with almost 100 % dechlorination at -1.0 V, far superior to that of traditional indirect reduction-driven commercial Pd/C (52 %) and direct reduction-driven Co1-N-C (44 %). Moreover, its dechlorination rate constant of 1.64 h-1 was 4.3 and 8.6 times more active than those of Pd/C (0.38 h-1) and Co1-N-C (0.19 h-1), respectively. Our research sheds light on the rational design of hydrogen spillover-related electrocatalysts to simultaneously improve the H* generation, transfer, and utilization for environmental and energy applications.

Harmonizing the cyano-group and Na to enhance selective photocatalytic O2 activation on carbon nitride for refractory pollutant degradation.

Manipulating exciton dissociation and charge-carrier transfer processes to selectively generate free radicals of more robust photocatalytic oxidation capacity for mineralizing refractory pollutants remains challenging. Herein, we propose a strategy by simultaneously introducing the cyano-group and Na into graphitic carbon nitride (CN) to obtain CN-Cy-Na, which makes the charge-carrier transfer pathways the dominant process and consequently achieves the selective generation of free radicals. Briefly, the cyano-group intensifies the local charge density of CN, offering a potential well to attract the hole of exciton, which accelerates the exciton dissociation. Meanwhile, the separated electron transfers efficiently under the robust built-in electric field induced by the cyano-group and Na, and eventually accumulates in the heptazine ring of CN for the following O2 reduction due to the reinforced electron sink effect caused by Na. As a result, CN-Cy-Na exhibits 4.42 mmol L-1 h-1 productivity with 97.6% selectivity for free radicals and achieves 82.1% total organic carbon removal efficiency in the tetracycline photodegradation within 6 h. Additionally, CN-Cy-Na also shows outstanding photodegradation efficiency of refractory pollutants, including antibiotics, pesticide plastic additives, and dyes. This work presents an innovative approach to manipulating the exciton effect and enhancing charge-carrier mobility within two-dimensional photocatalysts, opening an avenue for precise control of free radical generation.

Engineering the Coordination Environment of Ir Single Atoms with Surface Titanium Oxide Amorphization for Superior Chlorine Evolution Reaction.

The chlorine evolution reaction (CER) is essential for industrial Cl2 production but strongly relies on the use of dimensionally stable anode (DSA) with high-amount precious Ru/Ir oxide on a Ti substrate. For the purpose of sustainable development, precious metal decrement and performance improvement are highly desirable for the development of CER anodes. Herein, we demonstrate that surface titanium oxide amorphization is crucial to regulate the coordination environment of stabilized Ir single atoms for efficient and durable chlorine evolution of Ti monolithic anodes. Experimental and theoretical results revealed the formation of four-coordinated Ir1O4 and six-coordinated Ir1O6 sites on amorphous and crystalline titanium oxides, respectively. Interestingly, the Ir1O4 sites exhibited a superior CER performance, with a mass activity about 10 and 500 times those of the Ir1O6 counterpart and DSA, respectively. Moreover, the Ir1O4 anode displayed excellent durability for 200 h, far longer than that of its Ir1O6 counterpart (2 h). Mechanism studies showed that the unsaturated Ir in Ir1O4 was the active center for chlorine evolution, which was changed to the top-coordinated O in Ir1O6. This change of active sites greatly affected the adsorption energy of Cl species, thus accounting for their different CER activity. More importantly, the amorphous structure and restrained water dissociation of Ir1O4 synergistically prevent oxygen permeation across the Ti substrate, contributing to its long-term CER stability. This study sheds light on the importance of single-atom coordination structures in the reactivity of catalysts and offers a facile strategy to prepare highly active single-atom CER anodes via surface titanium oxide amorphization.

Spin polarized Fe1-Ti pairs for highly efficient electroreduction nitrate to ammonia.

Electrochemical nitrate reduction to ammonia offers an attractive solution to environmental sustainability and clean energy production but suffers from the sluggish *NO hydrogenation with the spin-state transitions. Herein, we report that the manipulation of oxygen vacancies can contrive spin-polarized Fe1-Ti pairs on monolithic titanium electrode that exhibits an attractive NH3 yield rate of 272,000 µg h-1 mgFe-1 and a high NH3 Faradic efficiency of 95.2% at -0.4 V vs. RHE, far superior to the counterpart with spin-depressed Fe1-Ti pairs (51000 µg h-1 mgFe-1) and the mostly reported electrocatalysts. The unpaired spin electrons of Fe and Ti atoms can effectively interact with the key intermediates, facilitating the *NO hydrogenation. Coupling a flow-through electrolyzer with a membrane-based NH3 recovery unit, the simultaneous nitrate reduction and NH3 recovery was realized. This work offers a pioneering strategy for manipulating spin polarization of electrocatalysts within pair sites for nitrate wastewater treatment.

[Responses of radial growth of Quercus mongolica to stand density and climatic factors in a mountainous area of eastern Liaoning Province, China]. / è¾½ä¸œå±±åŒºè’™å¤æ Žå¾„å‘ç”Ÿé•¿å¯¹æž—åˆ†å¯†åº¦å’Œæ°”å€™å› å­çš„å“åº”.

To explore the effects of stand density and climatic factors on radial growth of Quercus mongolica, we used tree ring chronology to examine the radial growth changes in a secondary Q. mongolica forest under different levels of stand density (thinning). The meteorological data combined with the driving factors of Q. mongolica growth were analyzed. The results showed that the radial growth of Q. mongolica was significantly affected by stand density. The mean annual radial growth of Q. mongolica was 3.12 mm in low-density virgin forest, 1.55 and 1.42 mm in the two medium-density secondary forests, respectively, and 0.96 mm in high-density secondary forest. The thinning intensity of 20% had a limited effect on promoting the radial growth recovery of high-density forest (1900 trees·hm-2), but had a significant effect on medium-density forest (1600 trees·hm-2). The radial growth of Q. mongolica was sensitive to the precipitation changes in January and February of the current year. Thinning reduced the sensitivity of Q. mongolica radial growth to climate. Under scenarios of climate warming and drying, density regulation could be beneficial in mitigating the adverse effects of climate change on the growth of Q. mongolica.

Effects of land use types on surface water quality across an anthropogenic disturbance gradient in the upper reach of the Hun River, Northeast China.

Surface water quality is vulnerable to pollution due to human activities. The upper reach of the Hun River is an important water source that supplies 52 % of the storage capacity of the Dahuofang Reservoir, the largest reservoir for drinking water in Northeast China, which is suffering from various human-induced changes in land use, including deforestation, reclamation/farming, urbanization and mine exploitation. To investigate the impacts of land use types on surface water quality across an anthropogenic disturbance gradient at a local scale, 11 physicochemical parameters (pH, dissolved oxygen [DO], turbidity, oxygen redox potential, conductivity, biochemical oxygen demand [BOD5], chemical oxygen demand [COD], total nitrogen [TN], total phosphorus [TP], NO(3)(-)N, and NH(4)(+)-N) of water from 12 sampling sites along the upper reach of the Hun River were monitored monthly during 2009-2010. The sampling sites were classified into four groups (natural, near-natural, more disturbed, and seriously disturbed). The water quality exhibited distinct spatial and temporal characteristics; conductivity, TN, and NO(3)(-)-N were identified as key parameters indicating the water quality variance. The forest and farmland cover types played significant roles in determining the surface water quality during the low-flow, high-flow, and mean-flow periods based on the results of a stepwise linear regression. These results may provide incentive for the local government to consider sustainable land use practices for water conservation.