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Recently developed solid-state catalysts can mediate carbon dioxide (CO 2 ) electroreduction to valuable products at high rates and selectivities. However, under commercially relevant current densities of > 200 milliamperes per square centimeter (mA cm −2 ), catalysts often undergo particle agglomeration, active-phase change, and/or element dissolution, making the long-term operational stability a considerable challenge. Here we report an indium sulfide catalyst that is stabilized by adding zinc in the structure and shows dramatically improved stability. The obtained ZnIn 2 S 4 catalyst can reduce CO 2 to formate with 99.3% Faradaic efficiency at 300 mA cm −2 over 60 h of continuous operation without decay. By contrast, similarly synthesized indium sulfide without zinc participation deteriorates quickly under the same conditions. Combining experimental and theoretical studies, we unveil that the introduction of zinc largely enhances the covalency of In-S bonds, which “locks” sulfur—a catalytic site that can activate H 2 O to react with CO 2 , yielding HCOO* intermediates—from being dissolved during high-rate electrolysis. Developing durable catalysts for carbon dioxide reduction to formate at commercial-scale current densities is challenging. This work reports that indium sulfide stabilized through zinc incorporation can produce formate efficiently and quickly at high current densities over long timescales.

Although much effort has been devoted to improving photoelectrochemical water splitting of hematite (α-Fe 2 O 3 ) due to its high theoretical solar-to-hydrogen conversion efficiency of 15.5%, the low applied bias photon-to-current efficiency remains a huge challenge for practical applications. Herein, we introduce single platinum atom sites coordination with oxygen atom (Pt-O/Pt-O-Fe) sites into single crystalline α-Fe 2 O 3 nanoflakes photoanodes (SAs Pt:Fe 2 O 3 -Ov). The single-atom Pt doping of α-Fe 2 O 3 can induce few electron trapping sites, enhance carrier separation capability, and boost charge transfer lifetime in the bulk structure as well as improve charge carrier injection efficiency at the semiconductor/electrolyte interface. Further introduction of surface oxygen vacancies can suppress charge carrier recombination and promote surface reaction kinetics, especially at low potential. Accordingly, the optimum SAs Pt:Fe 2 O 3 -Ov photoanode exhibits the photoelectrochemical performance of 3.65 and 5.30 mA cm −2 at 1.23 and 1.5 V RHE , respectively, with an applied bias photon-to-current efficiency of 0.68% for the hematite-based photoanodes. This study opens an avenue for designing highly efficient atomic-level engineering on single crystalline semiconductors for feasible photoelectrochemical applications. The achievable photocurrent of hematite, α-Fe 2 O 3 , is typically limited far below its theoretical limit. Here, the authors engineer single Pt atomic sites with surface oxygen vacancies into hematite photoanodes, which leads to enhanced photoelectrochemical water splitting.

Operating fuel cells in alkaline environments permits the use of platinum-group-metal-free (PGM-free) catalysts and inexpensive bipolar plates, leading to significant cost reduction. Of the PGM-free catalysts explored, however, only a few nickel-based materials are active for catalyzing the hydrogen oxidation reaction (HOR) in alkali; moreover, these catalysts deactivate rapidly at high anode potentials owing to nickel hydroxide formation. Here we describe that a nickel–tungsten–copper (Ni 5.2 WCu 2.2 ) ternary alloy showing HOR activity rivals Pt/C benchmark in alkaline electrolyte. Importantly, we achieved a high anode potential up to 0.3 V versus reversible hydrogen electrode on this catalyst with good operational stability over 20 h. The catalyst also displays excellent CO-tolerant ability that Pt/C catalyst lacks. Experimental and theoretical studies uncover that nickel, tungsten, and copper play in synergy to create a favorable alloying surface for optimized hydrogen and hydroxyl bindings, as well as for the improved oxidation resistance, which result in the HOR enhancement. The lack of efficient and cost-effective catalysts for H 2 oxidation reaction (HOR) hinders the application of anion exchange membrane fuel cells. Here, authors report a ternary nickel-tungsten-copper nanoalloy with marked HOR activity and stability that rivals the benchmark platinum catalyst.

Transition metal dichalcogenide materials have been explored extensively as catalysts to negotiate the hydrogen evolution reaction, but they often run at a large excess thermodynamic cost. Although activating strategies, such as defects and composition engineering, have led to remarkable activity gains, there remains the requirement for better performance that aims for real device applications. We report here a phosphorus-doping-induced phase transition from cubic to orthorhombic phases in CoSe 2 . It has been found that the achieved orthorhombic CoSe 2 with appropriate phosphorus dopant (8 wt%) needs the lowest overpotential of 104 mV at 10 mA cm −2 in 1 M KOH, with onset potential as small as −31 mV. This catalyst demonstrates negligible activity decay after 20 h of operation. The striking catalysis performance can be attributed to the favorable electronic structure and local coordination environment created by this doping-induced structural phase transition strategy. Transition metal dichalcogenides represent an exciting class of earth-abundant hydrogen-from-water electrocatalysts, although low efficiencies limit commercialization. Here, authors present a doping strategy to induce a phase transition in cobalt selenide and boost H 2 -evolution performance.

Layered molybdenum disulfide has demonstrated great promise as a low-cost alternative to platinum-based catalysts for electrochemical hydrogen production from water. Research effort on this material has focused mainly on synthesizing highly nanostructured molybdenum disulfide that allows the exposure of a large fraction of active edge sites. Here we report a promising microwave-assisted strategy for the synthesis of narrow molybdenum disulfide nanosheets with edge-terminated structure and a significantly expanded interlayer spacing, which exhibit striking kinetic metrics with onset potential of −103 mV, Tafel slope of 49 mV per decade and exchange current density of 9.62 × 10 −3 mA cm −2 , performing among the best of current molybdenum disulfide catalysts. Besides benefits from the edge-terminated structure, the expanded interlayer distance with modified electronic structure is also responsible for the observed catalytic improvement, which suggests a potential way to design newly advanced molybdenum disulfide catalysts through modulating the interlayer distance. Layered molybdenum disulfide is a promising hydrogen evolution catalyst. Here, the authors report a strategy for synthesizing molybdenum disulfide nanosheets with edge-terminated structure and a significantly expanded interlayer spacing and demonstrate their enhanced catalytic activity.

Singlet oxygen has won a great deal of attention to catalysis and biological studies due to its strong oxidizing properties. However, the photosensitizers which require for the generation of singlet oxygen remain inadequate because of their lack of long-wavelength absorption, weak hydrophilicity, and poor biocompatibility. Here, we develop near-infrared laser activated supramolecular photosensitizers (isophthalic acid/layered double hydroxide nanohybrids) for efficient two-photon photodynamic therapy. The singlet oxygen quantum yield of nanohybrid is up to 0.74. Critically, in vitro tests verify the superior anti-cancer properties of nanohybrid with an IC 50 determine to be 0.153 μg mL −1 . The nanohybrids take advantage of the superior tissue penetration of 808 nm laser irradiation and exhibit a dramatically strong ability to ablate tumors in vivo, with extremely low toxicity. This work provides the proof of concept that ultralong-lived triplet excitons can function as two-photon-activated photosensitizers for an effective singlet oxygen generation. Usually, several components are needed for efficient 2-photon photodynamic therapy (PDT). Here, the authors sandwiched carboxylic acids between layered double hydroxide nanosheets to obtain a single-handed biocompatible photosensitizer that generates singlet oxygen in high quantum yield.

The electroreduction of water for sustainable hydrogen production is a critical component of several developing clean-energy technologies, such as water splitting and fuel cells. However, finding a cheap and efficient alternative catalyst to replace currently used platinum-based catalysts is still a prerequisite for the commercialization of these technologies. Here we report a robust and highly active catalyst for hydrogen evolution reaction that is constructed by in situ growth of molybdenum disulfide on the surface of cobalt diselenide. In acidic media, the molybdenum disulfide/cobalt diselenide catalyst exhibits fast hydrogen evolution kinetics with onset potential of −11 mV and Tafel slope of 36 mV per decade, which is the best among the non-noble metal hydrogen evolution catalysts and even approaches to the commercial platinum/carbon catalyst. The high hydrogen evolution activity of molybdenum disulfide/cobalt diselenide hybrid is likely due to the electrocatalytic synergistic effects between hydrogen evolution-active molybdenum disulfide and cobalt diselenide materials and the much increased catalytic sites. There is substantial research into new catalysts for electroreduction of water. Here, the authors report a robust and active molybdenum disulfide/cobalt diselenide hydrogen evolution catalyst with onset potential of 11 mV and Tafel slope of 36 mV per decade, approaching the activity of platinum.

The lack of available protons severely lowers the activity of alkaline hydrogen evolution reaction process than that in acids, which can be efficiently accelerated by tuning the coverage and chemical environment of protons on catalyst surface. However, the cycling of active sites by proton transfer is largely dependent on the utilization of noble metal catalysts because of the appealing electronic interaction between noble metal atoms and protons. Herein, an all-non-noble W/WO 2 metallic heterostructure serving as an efficient solid-acid catalyst exhibits remarkable hydrogen evolution reaction performance with an ultra-low overpotential of −35 mV at −10 mA/cm 2 and a small Tafel slope (−34 mV/dec), as well as long-term durability of hydrogen production (>50 h) at current densities of −10 and −50 mA/cm 2 in alkaline electrolyte. Multiple in situ and ex situ spectroscopy characterizations combining with first-principle density functional theory calculations discover that a dynamic proton-concentrated surface can be constructed on W/WO 2 solid-acid catalyst under ultra-low overpotentials, which enables W/WO 2 catalyzing alkaline hydrogen production to follow a kinetically fast Volmer-Tafel pathway with two neighboring protons recombining into a hydrogen molecule. Our strategy of solid-acid catalyst and utilization of multiple spectroscopy characterizations may provide an interesting route for designing advanced all-non-noble catalytic system towards boosting hydrogen evolution reaction performance in alkaline electrolyte. The high cost and low abundance of noble metals largely restrict practical applications for electrochemical hydrogen production. Here, the authors prepare ultrasmall tungsten nanoparticles on metallic tungsten dioxide nanorods and demonstrate excellent activities for the alkaline hydrogen evolution reaction.

Simultaneously improving the activity and stability of catalysts for anodic oxygen evolution reaction (OER) in proton exchange membrane water electrolysis (PEMWE) remains a notable challenge. Here, we report a chromium-doped ruthenium dioxide with oxygen vacancies, termed Cr 0.2 Ru 0.8 O 2-x , that drives OER with an overpotential of 170 mV at 10 mA cm −2 and operates stably over 2000 h in acidic media. Experimental and theoretical studies show that the synergy of Cr dopant and oxygen vacancy induces an unconventional dopant-mediated hydroxyl spillover mechanism. Such dynamic hydroxyl spillover from Cr dopant to Ru active site changes the rate-determining step from OOH* formation to O 2 formation and thus greatly improves the OER performance. Moreover, the Cr dopant and oxygen vacancy also play a crucial role in stabilizing surface Ru and lattice oxygen in the Ru-O-Cr structural motif. When assembled into the anode of a practical PEMWE device, Cr 0.2 Ru 0.8 O 2-x enables long-term durability of over 200 h at an ampere-level current density and 60 degrees centigrade. Developing highly active and stable anode catalysts for green hydrogen production is crucial but challenging. Here, the authors report a Cr0.2Ru0.8O2-x catalyst with an unconventional dopant-mediated hydroxyl spillover mechanism for high-efficiency proton exchange membrane water electrolysis.

Hydroxide exchange membrane fuel cells offer possibility of adopting platinum-group-metal-free catalysts to negotiate sluggish oxygen reduction reaction. Unfortunately, the ultrafast hydrogen oxidation reaction (HOR) on platinum decreases at least two orders of magnitude by switching the electrolytes from acid to base, causing high platinum-group-metal loadings. Here we show that a nickel-molybdenum nanoalloy with tetragonal MoNi 4 phase can catalyze the HOR efficiently in alkaline electrolytes. The catalyst exhibits a high apparent exchange current density of 3.41 milliamperes per square centimeter and operates very stable, which is 1.4 times higher than that of state-of-the-art Pt/C catalyst. With this catalyst, we further demonstrate the capability to tolerate carbon monoxide poisoning. Marked HOR activity was also observed on similarly designed WNi 4 catalyst. We attribute this remarkable HOR reactivity to an alloy effect that enables optimum adsorption of hydrogen on nickel and hydroxyl on molybdenum (tungsten), which synergistically promotes the Volmer reaction. The lack of efficient and cost-effective catalysts for hydrogen oxidation reaction (HOR) hampers the application of hydroxide exchange membrane fuel cells. Here, authors reported bimetallic MoNi 4 and WNi 4 nanoalloys with marked HOR activity in alkali, among which MoNi4 outperforms the Pt/C catalyst.