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The formation and preservation of the active phase of the catalysts at the triple-phase interface during CO2 capture and reduction is essential for improving the conversion efficiency of CO2 electroreduction toward value-added chemicals and fuels under operational conditions. Designing such ideal catalysts that can mitigate parasitic hydrogen generation and prevent active phase degradation during the CO2 reduction reaction (CO2RR), however, remains a significant challenge. Herein, we developed an interfacial engineering strategy to build a new SnOx catalyst by invoking multiscale approaches. This catalyst features a hierarchically nanoporous structure coated with an organic F-monolayer that modifies the triple-phase interface in aqueous electrolytes, substantially reducing competing hydrogen generation (less than 5%) and enhancing CO2RR selectivity (∼90%). This rationally designed triple-phase interface overcomes the issue of limited CO2 solubility in aqueous electrolytes via proactive CO2 capture and reduction. Concurrently, we utilized pulsed square-wave potentials to dynamically recover the active phase for the CO2RR to regulate the production of C1 products such as formate and carbon monoxide (CO). This protocol ensures profoundly enhanced CO2RR selectivity (∼90%) compared with constant potential (∼70%) applied at -0.8 V (V vs RHE). We further achieved a mechanistic understanding of the CO2 capture and reduction processes under pulsed square-wave potentials via in situ Raman spectroscopy, thereby observing the potential-dependent intensity of Raman vibrational modes of the active phase and CO2RR intermediates. This work will inspire material design strategies by leveraging triple-phase interface engineering for emerging electrochemical processes, as technology moves toward electrification and decarbonization.

Proton-exchange membrane water electrolyzers (PEMWEs) are a promising technology for green hydrogen production; however, interfacial transport behaviors are poorly understood, hindering device performance and longevity. Here, we first utilized finite-gap electrolyzer to demonstrate the possibility of proton transfer through water in PEMWEs. The measured high-frequency resistances (HFRs) exhibit a linear trend with increasing gap distance, where extrapolation shows a lower value compared with HFRs in regular zero-gap electrolyzers, indicating that ohmic resistance could be further reduced. We introduce nanochannels to facilitate mass transport, as evidenced by both liquid-fed and vapor-fed electrolysis. Nanochannel electrodes achieve a voltage reduction of 190 mV at 9 A·cm−2 compared with the Ir-PTEs without nanochannels. Furthermore, nanochannel electrodes show negligible degradation through 100,000 accelerated-stress tests and over 2,000 h of operation at 1.8 A·cm−2 with a decay rate of 11.66 μV·h−1. These results provide new insights into localized transport dynamics for PEMWEs and highlight the significance of interfacial engineering for electrochemical devices.

Two simple processes for enhancing liquid alkaline water electrolyzer performance are demonstrated. Both enhance 3D Ni electrodes by introducing a micron-scale rough structure throughout the bulk of the electrode. Oxidation/reduction relies on a simple thermal treatment cycle to create surface roughening through the volumetric expansion during NiO formation and volume contraction during reduction back to Ni metal. Catalyst infiltration introduces a washcoat of additional metal particles throughout the electrode, by flooding the electrode with catalyst precursor and converting it to micron-scale particles via a reducing thermal treatment. The largest improvement in performance (211 mV at 1.8 A cm−2) is observed for infiltrated NiFe-3x catalyst. For Fe-free Ni-only electrodes, oxidation/reduction provides a larger improvement (157 mV at 1.8 A cm−2) than infiltrated Ni-3X (106 mV at 1.8 A cm−2). For both processes, the observed electrode surface structure and performance is quite sensitive to the thermal treatment temperature.

Green hydrogen, produced via water electrolysis using renewable electricity, will play a crucial role in decarbonizing industrial and heavy-duty transportation sectors. Anion exchange membrane water electrolyzers (AEMWEs) can overcome many of the performance and cost limitations of incumbent technologies, however, still suffer from durability challenges due to oxidative instability of anion-exchange ionomers. Herein, the use of an electro-active porous transport layer as anode (PTL-electrode) is demonstrated to enable efficient and durable AEMWEs. The stainless-steel PTL-electrodes are shown to have superior performance and durability compared to traditional catalyst layers containing ionomer and nanoparticle catalysts. An AEMWE cell operating at 2 A cm−2 for over 600 h exhibited a degradation rate of just 5 µV h−1. During operation, the surface composition of the stainless steel transforms into a mixture of iron and nickel oxyhydroxides, contributing to enhanced oxygen-evolution reaction activity. The combination of experimental work and modeling elucidates how the bulk structure of the PTL-electrode offers an additional design dimension to further improve electrolyzer performance. Lastly, a surface modification strategy is applied to a PTL-electrode to achieve an even higher performing AEMWE (2.3 vs 2.0 A cm−2 at 1.8 V). Overall, this work lays out pathways toward more efficient, durable, and affordable AEMWEs.

【Objective】 The increased demand for water due to economic development coupled with dwindling water supply is the double whammy facing most provinces in north China. Given agriculture is the biggest water use sector, understanding the change in agricultural water demand is critical to improving water resources management. The purpose of this paper is to present a new method to estimate agricultural water use changes at provincial scale in the north of China. 【Method】 The proposed method was based on discrete wavelet transform (DWT), fractional-order grey model (FGM(1,1)), weighted Markov Chain (WMC), and autoregressive moving average (ARMA) model. The time series of agricultural water demand was firstly decomposed into approximate series and detailed series, respectively, using DWT. FGM(1,1) was then used to describe the approximate series, with the errors corrected by WMC. The Fisher optimal segmentation method was used to divide the state intervals of the predicted errors, and the state intervals were predicted using a probability transfer matrix. The predicted intervals and values of the approximate series were obtained from the boundary values and median of the predicted error state intervals. In comparison, the detailed series were predicted using the ARMA model based on the Akaike Information Criteria. These were used to predict the agricultural water demand and its intervals. We applied the models to agricultural water demand in Shaanxi and Inner Mongolia provinces, with data measured from 2002 to 2015 used to train the model and those measured from 2016 to 2019 to validate the model. We compared the results calculated from the proposed model with those estimated from the traditional GM (1,1), DWT- GM(1,1)-ARMA, and DWT-FGM(1,1)-ARMA models. 【Result】 The average absolute error of the proposed model for the two provinces was 1.25% and 1.01%, respectively, much less than those given rise to by other models. The predicted agricultural water demand intervals showed that after correction by WMC, the model provided reliable short-term fluctuation intervals in agricultural water demand in both provinces. 【Conclusion】 The proposed model for predicting agricultural water demand at provincial scale was accurate and robust. It can also predict the intervals which describe the short-term fluctuation in agricultural water demand. The model has an implication in helping improve water management and developing sustainable agriculture.

The Xujiashan Sb deposit located at the Mufushan fold thrust belt of the Yangtze block is one of the most important Sb deposits in this district. Stibnite in this deposit contains high and various contents of Se, but research on the distribution and enrichment of Se in stibnite remains limited. This paper conducts geochemical composition, C-H-O isotopic composition, and scanning electron microscopy morphology of the Xujiashan deposit to discuss the sources of ore-forming materials and fluid, as well as the distribution and enrichment mechanisms of selenium in stibnite. The results showed that the ores have trace element compositions comparable with the wall rocks, and Sb and Se contents are significantly higher than the average carbonate rocks. The δ13CPDB values of calcite and quartz range from −12.8‰ to 5.5‰, the δ18OSMOW values range from 20.4‰ to 24‰, and the δDV-SMOW values range from −57.8‰ to −86.9‰. Trace element and isotope compositions indicate that the ore-forming materials were mainly derived from the wall rocks (sedimentary–metamorphic rocks) that S, Se, and Sb dissolved during fluid–rock interactions. The ore-forming fluids were metamorphic water produced by metamorphism, which had experienced multistage mixing with meteoric water and organic-rich fluids. Selenium substitutes for sulfur in the stibnite crystal lattice, causing rhythmically distributed Se contents in stibnite, which resulted from multistage physicochemical changes in ore-forming fluids during crystallization. The varied patterns of Se contents are the result of different cross-sections of the stibnite. [ABSTRACT FROM AUTHOR]

Solid-state electrolytes (SSEs) play a vital role in the development of high-energy all-solid-state batteries. However, most adopted mechanical ball milling and/or high-temperature annealing are ineffective approaches for large-scale synthesis. Herein, a universal and scalable hydrate-assisted strategy for the synthesis of oxychloride SSEs is developed based on the chemical reaction among alkali chlorides, AlCl 3 , and AlCl 3 ·6H 2 O. The synthesized aluminum-based oxychloride SSEs possess a high Li + conductivity over 1 mS cm -1 at 30 °C. The final aluminum-based oxychloride SSEs are structurally heterogeneous with nm-sized LiCl-like and LiAlCl 4 crystallites and large amounts of amorphous [Al a O b Cl c ] (2 b + c -3 a )- components. Faster local mobility of Li + ions in amorphous structures is verified and is attributable to weakened Li + -X - interactions ensured by the [Al a O b Cl c ] (2 b + c -3 a )- polyanions. The potential applications for this synthesis technique are further demonstrated by kilogram-scale reactions and synthesis of other oxychloride SSEs including zirconium-based and tantalum-based analogs. These findings not only provide a new simple, scalable, and energy-efficient synthesis route for oxychloride SSEs but also further promote their application in all-solid-state batteries., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

The formation and preservation of the active phase of the catalysts at the triple-phase interface during CO 2 capture and reduction is essential for improving the conversion efficiency of CO 2 electroreduction toward value-added chemicals and fuels under operational conditions. Designing such ideal catalysts that can mitigate parasitic hydrogen generation and prevent active phase degradation during the CO 2 reduction reaction (CO 2 RR), however, remains a significant challenge. Herein, we developed an interfacial engineering strategy to build a new SnO x catalyst by invoking multiscale approaches. This catalyst features a hierarchically nanoporous structure coated with an organic F-monolayer that modifies the triple-phase interface in aqueous electrolytes, substantially reducing competing hydrogen generation (less than 5%) and enhancing CO 2 RR selectivity (∼90%). This rationally designed triple-phase interface overcomes the issue of limited CO 2 solubility in aqueous electrolytes via proactive CO 2 capture and reduction. Concurrently, we utilized pulsed square-wave potentials to dynamically recover the active phase for the CO 2 RR to regulate the production of C1 products such as formate and carbon monoxide (CO). This protocol ensures profoundly enhanced CO 2 RR selectivity (∼90%) compared with constant potential (∼70%) applied at -0.8 V (V vs RHE). We further achieved a mechanistic understanding of the CO 2 capture and reduction processes under pulsed square-wave potentials via in situ Raman spectroscopy, thereby observing the potential-dependent intensity of Raman vibrational modes of the active phase and CO 2 RR intermediates. This work will inspire material design strategies by leveraging triple-phase interface engineering for emerging electrochemical processes, as technology moves toward electrification and decarbonization.