Heterostructure engineering plays a vital role in regulating the material interface, thus boosting the electron transportation pathway in advanced catalysis. Herein, a novel Bi2O3/BiO2 heterojunction catalyst was synthesized via a molten alkali-assisted dealumination strategy and exhibited rich structural dynamics for an electrocatalytic CO2 reduction reaction (ECO2RR). By coupling in situ X-ray diffraction and Raman spectroscopy measurements, we found that the as-synthesized Bi2O3/BiO2 heterostructure can be transformed into a novel Bi/BiO2 Mott–Schottky heterostructure, leading to enhanced adsorption performance for CO2 and *OCHO intermediates. Consequently, high selectivity toward formate larger than 95% was rendered in a wide potential window along with an optimum partial current density of −111.42 mA cm–2 that benchmarked with the state-of-the-art Bi-based ECO2RR catalysts. This work reports the construction and fruitful structural dynamic insights of a novel heterojunction electrocatalyst for ECO2RR, which paves the way for the rational design of efficient heterojunction electrocatalysts for ECO2RR and beyond.

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The high‐throughput scalable production of inexpensive and efficient electrode materials at high current densities demanded by industry is a huge challenge for large‐scale implementation of energy storage technologies. Here, inspired by theoretical calculations that a FeS2/TiO2 heterostructure with built‐in electric field (BEF) can reduce the reaction energy barrier and enhance charge transport, the scalable production of cheap FeS2/TiO2 heterostructure is fabricated by utilizing natural ilmenite as precursor, exhibiting excellent electrochemical performances for sodium‐ion capacitors (SICs) anode. Assembling it with activated carbon (AC) cathode for SICs delivers high energy density (73.7 Wh kg−1) and high power density (10 kW kg−1) as well as outstanding cycle lifespan. Impressively, the method breaks through the traditional preparation approach by using natural minerals instead of high‐purity chemical raw materials as precursors for constructing heterojunctions, and price of the mineral is nearly five orders of magnitude lower than that of commercial chemical raw materials with high‐purity, which greatly reduces raw materials cost and is available for mass production. Similarly, the method can be extended to utilize other minerals to construct heterostructures, thus achieving expanded electrochemical performance, which exhibits huge potentials in electrochemical energy storage.

Ultrathin two-dimensional (2D) metal oxyhalides exhibit outstanding photocatalytic properties with unique electronic and interfacial structures. Compared with monometallic oxyhalides, bimetallic oxyhalides are less explored. In this work, we have developed a novel top-down wet-chemistry desalination approach to remove the alkali-halide salt layer within the complicated precursor bulk structural matrix Pb0.6Bi1.4Cs0.6O2Cl2, and successfully fabricate a new 2D ultrathin bimetallic oxyhalide Pb0.6Bi1.4O2Cl1.4. The unlocked larger surface area, rich bimetallic active sites, and faster carrier dynamics within Pb0.6Bi1.4O2Cl1.4 layers significantly enhance the photocatalytic efficiency for atmospheric CO2 reduction. It outperforms the corresponding parental matrix phase and other state-of-the-art bismuth-based monometallic oxyhalides photocatalysts. This work reports a top-down desalination strategy to engineering ultrathin bimetallic 2D material for photocatalytic atmospheric CO2 reduction, which sheds light on further constructing other ultrathin 2D catalysts for environmental and energy applications from similar complicate structure matrixes.

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Developing earth-abundant, active, and stable electrocatalysts for hydrogen evolution reactions (HERs) at large current densities has remained challenging. Herein, heterostructured nickel foam-supported cobalt carbonate hydroxide nanoarrays embellished with NiCoS x nanoflakes (NiCoS x @CoCH NAs/NF) are designed via room-temperature sulfurization, which can drive 10 and 1000 mA cm −2 at low overpotentials of 55 and 438 mV for HER and exhibit impressive long-term stability at the industrial-level current density. Surprisingly, NiCoS x @CoCH NAs/NF after a 500 h stability test at 500 mA cm −2 exhibit better catalytic performance than the initial one at high current densities. Simulations showed that NiCoS x @CoCH NAs have an optimized hydrogen adsorption free energy (ΔG H* ) of 0.02 eV, owing to the synergistic effect of CoCH (ΔG H* = 1.36 eV) and NiCoS x (ΔG H* = 0.03 eV). The electric field at the heterostructure interface leads to electron transport from CoCH to NiCoS x , which enhances HER dynamics. The hierarchical nanostructure has a large specific area and a superaerophobic surface, which are beneficial to hydrogen generation/release for efficient and stable HER.

The sustainable production of green hydrogen via water electrolysis necessitates cost-effective electrocatalysts. By following the circular economy principle, the utilization of waste-derived catalysts significantly promotes the sustainable development of green hydrogen energy. Currently, diverse waste-derived catalysts have exhibited excellent catalytic performance toward hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and overall water electrolysis (OWE). Herein, we systematically examine recent achievements in waste-derived electrocatalysts for water electrolysis. The general principles of water electrolysis and design principles of efficient electrocatalysts are discussed, followed by the illustration of current strategies for transforming wastes into electrocatalysts. Then, applications of waste-derived catalysts (i.e., carbon-based catalysts, transitional metal-based catalysts, and carbon-based heterostructure catalysts) in HER, OER, and OWE are reviewed successively. An emphasis is put on correlating the catalysts’ structure–performance relationship. Also, challenges and research directions in this booming field are finally highlighted. This review would provide useful insights into the design, synthesis, and applications of waste-derived electrocatalysts, and thus accelerate the development of the circular economy-driven green hydrogen energy scheme.

Iron-based nanosized ecomaterials for efficient Cr(VI) removal are of great interest to environmental chemists. Herein, inspired by the "mixed redox-couple" cations involved in the crystal structure and the quantum confinement effects resulting from the particle size, a novel type of iron-based ecomaterial, semiconducting chalcopyrite quantum dots (QDs), was developed and used for Cr(VI) removal. A high removal capacity up to 720 mg/g was achieved under optimal pH conditions, which is superior to those of the state-ofthe-art nanomaterials for Cr(VI) removal. The mechanism of Cr(VI) removal was elucidated down to an atomic scale by combining comprehensive characterization techniques with adsorption kinetic experiments and DFT calculations. The experimental results revealed that the material was a good electron donor semiconductor attributed to the existence of "mixed redox couple of Cu(I)-S-Fe(III)" in the crystal structure. With the size-dependent quantum confinement effect and the high surface area, the semiconducting chalcopyrite QDs could effectively remove Cr(VI) from aqueous solution through a syngenetic photocatalytic reduction and adsorption mechanism. This study not only reports the design histogram of the iron-based CuFeS 2 QD ecomaterial for efficient Cr(VI) removal but also paves the way for understanding the atomic-scale mechanism behind the syngenetic effects of using the QD semiconducting material for Cr(VI) removal.