Sub-10-nm-sized Au@AuxIr1-x metal-core/alloy-shell nanoparticles as highly durable catalysts for acidic water splitting.

The absence of efficient and durable catalysts for oxygen evolution reaction (OER) is the main obstacle to hydrogen production through water splitting in an acidic electrolyte. Here, we report a controllable synthesis method of surface IrOx with changing Au/Ir compositions by constructing a range of sub-10-nm-sized core-shell nanocatalysts composed of an Au core and AuxIr1-x alloy shell. In particular, Au@Au0.43Ir0.57 exhibits 4.5 times higher intrinsic OER activity than that of the commercial Ir/C. Synchrotron X-ray-based spectroscopies, electron microscopy and density functional theory calculations revealed a balanced binding of reaction intermediates with enhanced activity. The water-splitting cell using a load of 0.02 mgIr/cm2 of Au@Au0.43Ir0.57 as both anode and cathode can reach 10 mA/cm2 at 1.52 V and maintain activity for at least 194 h, which is better than the cell using the commercial couple Ir/C‖Pt/C (1.63 V, 0.2 h).

Electrochemical Evolution of Ru-Based Polyoxometalates into Si,W-Codoped RuOx for Acidic Overall Water Splitting.

Despite intensive studies over decades, the development of electrocatalysts for acidic water splitting still relies on platinum group metals, especially Pt and Ir, which are scarce, expensive, and poorly sustainable. Because such problems can be alleviated, Ru-based bifunctional catalysts such as rutile RuO2 have recently emerged. However, RuO2 has a relatively low activity for hydrogen evolution reactions (HER) and low stability for oxygen evolution reactions (OER) under acidic conditions. In this study, the synthesis of a RuOx -based bifunctional catalyst (RuSiW) for acidic water splitting via the electrochemical evolution from Ru-based polyoxometalates at cathodic potentials is reported. RuSiW consists of the nanocrystalline RuO2 core and Si,W-codoped RuOx shell. RuSiW exhibits outstanding HER and OER activity comparable to Pt/C and RuO2 , respectively, with high stability. Computational analysis suggests that the codoping of RuOx with W and Si synergistically improves the HER activity of otherwise poor RuO2 by shifting the d-band center and optimizing atomic configurations beneficial for proper hydrogen adsorption. This study provides insights into the design and synthesis of unprecedented bifunctional electrocatalysts using catalytically inactive and less explored elements, such as Si and W.

Breaking the Ru-O-Ru Symmetry of a RuO2 Catalyst for Sustainable Acidic Water Oxidation.

Proton exchange membrane water electrolysis is a highly promising hydrogen production technique for sustainable energy supply, however, achieving a highly active and durable catalyst for acidic water oxidation still remains a formidable challenge. Herein, we propose a local microenvironment regulation strategy for precisely tuning In-RuO2 /graphene (In-RuO2 /G) catalyst with intrinsic electrochemical activity and stability to boost acidic water oxidation. The In-RuO2 /G displays robust acid oxygen evolution reaction performance with a mass activity of 671 A gcat -1 at 1.5 V, an overpotential of 187 mV at 10 mA cm-2 , and long-lasting stability of 350 h at 100 mA cm-2 , which arises from the asymmetric Ru-O-In local structure interactions. Further, it is unraveled theoretically that the asymmetric Ru-O-In structure breaks the thermodynamic activity limit of the traditional adsorption evolution mechanism which significantly weakens the formation energy barrier of OOH*, thus inducing a new rate-determining step of OH* absorption. Therefore, this strategy showcases the immense potential for constructing high-performance acidic catalysts for water electrolyzers.

Porous Tellurium-Doped Ruthenium Dioxide Nanotubes for Enhanced Acidic Water Oxidation.

Electrocatalysts with high activity and durability for acidic oxygen evolution reaction (OER) play a crucial role in achieving cost-effective hydrogen production via proton exchange membrane water electrolysis. A novel electrocatalyst, Te-doped RuO2 (Te-RuO2 ) nanotubes, synthesized using a template-directed process, which significantly enhances the OER performance in acidic media is reported. The Te-RuO2 nanotubes exhibit remarkable OER activity in acidic media, requiring an overpotential of only 171 mV to achieve an anodic current density of 10 mA cm-2 . Furthermore, they maintain stable chronopotentiometric performance under 10 mA cm-2 in acidic media for up to 50 h. Based on the experimental results and density functional calculations, this significant improvement in OER performance to the synergistic effect of large specific surface area and modulated electronic structure resulting from the doping of Te cations is attributed.

Responses of diatom composition and teratological forms to environmental pollution in a post-mining lake (SW Poland).

Various types of environmental stressors, such as heavy metals, lignite residues, or extremely low water pH, cause the formation of teratological forms of diatoms during the reproductive cycle. The damage mainly includes an abnormal diatom valve outline, changes in the striation pattern, anomalies in the raphe line/sternum, reduction in the cell size, metabolism alterations, or combined deformities. Diatom remains with such morphological deformities occur in the sediments of post-mining lake LK-46 (SW Poland). This lake was formed by excavation after the end of lignite exploitation in the mid-1960s. The percentage of teratological valves in the studied lake ranged from 12 to 33% of the relative abundance. The majority of abnormal diatoms have been observed in species of Eunotia. The reconstruction of the diatom-inferred pH (DI-pH), together with the concentration of heavy metals in the sediments and contemporary measurements of the water pH, indicates that the lake was contaminated to varying degrees and was acidic from the beginning of lake creation until today. The lake is located in an area of acid mine drainage (AMD), and in its vicinity, there are overburden heaps containing lignite residues, which are eroded and supplied to the lake, constantly acidifying the water. In the youngest sediments, the concentration of heavy metals increased, while the percentage of abnormal diatoms decreased. Determining which factor, i.e., extremely low water pH and the presence of lignite or heavy metals, was responsible for the formation or reduction of teratogenic forms of diatoms is very difficult.

Optimal Coatings of Co3 O4 Anodes for Acidic Water Electrooxidation.

Implementation of proton-exchange membrane water electrolyzers for large-scale sustainable hydrogen production requires the replacement of scarce noble-metal anode electrocatalysts with low-cost alternatives. However, such earth-abundant materials often exhibit inadequate stability and/or catalytic activity at low pH, especially at high rates of the anodic oxygen evolution reaction (OER). Here, the authors explore the influence of a dielectric nanoscale-thin oxide layer, namely Al2 O3 , SiO2 , TiO2 , SnO2 , and HfO2 , prepared by atomic layer deposition, on the stability and catalytic activity of low-cost and active but insufficiently stable Co3 O4 anodes. It is demonstrated that the ALD layers improve both the stability and activity of Co3 O4 following the order of HfO2 > SnO2 > TiO2 > Al2 O3 , SiO2 . An optimal HfO2 layer thickness of 12 nm enhances the Co3 O4 anode durability by more than threefold, achieving over 42 h of continuous electrolysis at 10 mA cm-2 in 1 m H2 SO4 electrolyte. Density functional theory is used to investigate the superior performance of HfO2 , revealing a major role of the HfO2 |Co3 O4 interlayer forces in the stabilization mechanism. These insights offer a potential strategy to engineer earth-abundant materials for low-pH OER catalysts with improved performance from earth-abundant materials for efficient hydrogen production.

In Situ Activation Endows Orthorhombic Fluorite-Type Samarium Iridium Oxide with Enhanced Acidic Water Oxidation.

Developing electrochemical catalysts for acidic water oxidation with improved activity and stability has been the key to the further popularization of proton exchange membrane electrolyzers. In this work, an orthorhombic fluorite-type samarium iridium oxide (Sm3IrO7) catalyst is synthesized by a simple solid-state reaction. After in situ activation, the as-prepared Sm3IrO7 exhibits higher mass activity and durability than that of commercial IrO2. The in-depth analyses indicate the formation of amorphous IrOx species on the surface to evolve to a new heterostructure IrOx/Sm3IrO7, along with Sm leaching during the in situ activation process. More importantly, strong electronic interactions exist between newborn IrOx species and remaining Sm3IrO7, leading to the compressed Ir-O bonds in IrOx compared to commercial IrO2, thus reducing the energy barrier for oxygen evolution reaction (OER) intermediates to improve the OER process. Based on the above-mentioned analyses, it is speculated that the actual active species for enhanced acidic water oxidation should be IrOx/Sm3IrO7, rather than Sm3IrO7 itself. Theoretical calculations confirm that the optimal energy level path of IrOx/Sm3IrO7 follows the lattice oxygen mechanism, and the energy level of surface Ir 5d orbitals is lower than O 2p orbitals in IrOx/Sm3IrO7, enabling it a superior OER activity.

Metal-oxo Cluster Mediated Atomic Rh with High Accessibility for Efficient Hydrogen Evolution.

Achieving single-atom catalysts (SACs) with high metal content and outstanding performance as well as robust stability is critically needed for clean and sustainable energy. However, most of the synthesized SACs are undesired on the loading content of the metal due to the anchored metals and the supports as well as the synthesizing methods. Herein, a Rh-SAC with high accessibility by loading it on the metal nodes of metal-porphyrin-based PCN MOFs (PCN-224) as supporting material is reported. Significantly, the PCN-Rh15.9 /KB catalyst with a high Rh content of 15.9 wt% exhibits excellent hydrogen evolution activity with a low overpotential of 25 mV at a current density of 10 mA cm-2 and a mass activity of 7.7 A mg-1 Rh at overpotential of 150 mV, which is much better than that of the commercial Rh/C. Various characterizations reveal the Rh species is stabilized by the metal nodes bearing -O/OHx in MOFs, which is of importance for the high loading amount and the good activity. This work establishes an efficient approach to synthesize high content SACs on the nodes of MOFs for wide catalyst design.

Iridium-Catalyzed and pH-Dependent Reductions of Nitroalkenes to Ketones.

A highly chemoselective conversion of α,ß-disubstituted nitroalkenes to ketones is developed. An acid-compatible iridium catalyst serves as the key to the conversion. At a 2500 S/C ratio, nitroalkenes were readily converted to ketones in up to 72% isolated yields. A new mechanistic mode involving the reduction of nitroalkene to nitrosoalkene and N-alkenyl hydroxylamine is proposed. This conversion is ready to amplify to a gram-scale synthesis. The pH value plays an indispensable role in controlling the chemoselectivity.

Nanoscale TiO2 Coatings Improve the Stability of an Earth-Abundant Cobalt Oxide Catalyst during Acidic Water Oxidation.

The large-scale deployment of proton-exchange membrane water electrolyzers for high-throughput sustainable hydrogen production requires transition from precious noble metal anode electrocatalysts to low-cost earth-abundant materials. However, such materials are commonly insufficiently stable and/or catalytically inactive at low pH, and positive potentials required to maintain high rates of the anodic oxygen evolution reaction (OER). To address this, we explore the effects of a dielectric nanoscale-thin layer, constituted of amorphous TiO2, on the stability and electrocatalytic activity of nanostructured OER anodes based on low-cost Co3O4. We demonstrate a direct correlation between the OER performance and the thickness of the atomic layer deposited TiO2 layers. An optimal TiO2 layer thickness of 4.4 nm enhances the anode lifetime by a factor of ca. 3, achieving 80 h of continuous electrolysis at pH near zero, while preserving high OER catalytic activity of the bare Co3O4 surface. Thinner and thicker TiO2 layers decrease the stability and activity, respectively. This is attributed to the pitting of the TiO2 layer at the optimal thickness, which allows for access to the catalytically active Co3O4 surface while stabilizing it against corrosion. These insights provide directions for the engineering of active and stable composite earth-abundant materials for acidic water splitting for high-throughput hydrogen production.

Nitrogen-doped carbon armored Cobalt oxide hollow nanocubes electrochemically anchored on fluorine-doped tin oxide substrate for acidic oxygen evolution reaction.

Developments of non-precious metal based active and stable catalysts are of great importance and challenge to green hydrogen production from acidic electrocatalytic water splitting. Design of composite catalysts with synergy between active and stable components proves to be a promising approach. Herein, N-doped carbon armored Co3O4 hollow nanocubes electrochemically anchored on fluorine-doped tin oxide (FTO) substrates are developed as efficient and stable catalysts for acidic oxygen evolution reactions. Co3O4 acts as the active component with N-doped carbon coating layer serving as the stable protection component, shielding Co3O4 from direct attack of anodic dissolution. Electrochemical fixation offers firm holding of the composite catalyst onto acid-tolerant FTO substrates and hollow nanocubes serve as nano-reactors for confined fast reactions. Under optimal conditions, the composite catalyst achieves an overpotential of 465 mV at 10 mA cm-2 in 0.5 M H2SO4, and stays stable for 12 hr with a 10% increment in applied potentials.

Bifunctional WC-Supported RuO2 Nanoparticles for Robust Water Splitting in Acidic Media.

We report the strong catalyst-support interaction in WC-supported RuO2 nanoparticles (RuO2 -WC NPs) anchored on carbon nanosheets with low loading of Ru (4.11 wt.%), which significantly promotes the oxygen evolution reaction activity with a η10 of 347 mV and a mass activity of 1430 A gRu -1 , eight-fold higher than that of commercial RuO2 (176 A gRu -1 ). Theoretical calculations demonstrate that the strong catalyst-support interaction between RuO2 and the WC support could optimize the surrounding electronic structure of Ru sites to reduce the reaction barrier. Considering the likewise excellent catalytic ability for hydrogen production, an acidic overall water splitting (OWS) electrolyzer with a good stability constructed by bifunctional RuO2 -WC NPs only requires a cell voltage of 1.66 V to afford 10 mA cm-2 . The unique 0D/2D nanoarchitectures rationally combining a WC support with precious metal oxides provides a promising strategy to tradeoff the high catalytic activity and low cost for acidic OWS applications.

Iridium in Tungsten Trioxide Matrix as an Efficient Bi-Functional Electrocatalyst for Overall Water Splitting in Acidic Media.

Electrocatalytic water splitting in acidic media is a promising strategy for grid scale production of hydrogen using renewable energy, but challenges still exist in the development of advanced catalysts with both high activity and stability. Herein, it is reported that iridium doped tungsten trioxide (Ir-doped WO3 ) with arrayed structure and confined Ir sites is an efficient and durable bi-functional catalyst for overall acidic water splitting. A low overpotential (258 mV) is required to achieve an oxygen evolution reaction current density of 10 mA cm-2 in 0.5 m H2 SO4 solution. Meanwhile, Ir-doped WO3 processes a similar intrinsic activity to Pt/C toward hydrogen evolution reaction. Overall water splitting using the bi-functional Ir-doped WO3 catalyst shows low cell voltages of 1.56 and 1.68 V to drive the current densities of 10 and 100 mA cm-2 , respectively, with only 16 mV decay observed after 60 h continuous electrolysis under the current density of 100 mA cm-2 . Structural analysis and density functional theory calculation indicate that the adjusted coordination environment of Ir within the crystalline matrix of WO3 contributes to the high activity and durability.

Regulative Electronic States around Ruthenium/Ruthenium Disulphide Heterointerfaces for Efficient Water Splitting in Acidic Media.

Theoretical calculations unveil the charge redistribution over abundant interfaces and the enhanced electronic states of Ru/RuS2 heterostructure. The resulting surface electron-deficient Ru sites display optimized adsorption behavior toward diverse reaction intermediates, thereby reducing the thermodynamic energy barriers. Experimentally, for the first time the laminar Ru/RuS2 heterostructure is rationally engineered by virtue of the synchronous reduction and sulfurization under eutectic salt system. Impressively, it exhibits extremely high catalytic activity for both OER (201 mV @ 10 mA cm-2 ) and HER (45 mV @ 10 mA cm-2 ) in acidic media due to favorable kinetics and excellent specific activity, consequently leading to a terrific performance in acidic overall water splitting devices (1.501 V @ 10 mA cm-2 ). The in-depth insight into the internal activity origin of interfacial effect could offer precise guidance for the rational establishment of hybrid interfaces.

The removal of arsenic and metals from highly acidic water in horizontal subsurface flow constructed wetlands with alternative supporting media.

A laboratory-scale horizontal subsurface flow constructed wetland system was used to quantify the arsenic removal capacity in the treatment of highly acidic, arsenic and metal-rich water: pH ≈ 2, Fe ≈ 57 mg/L, Pb ≈ 0.9 mg/L, Zn ≈ 12 mg/L. The system was operated in two stages, being As ≈ 2.1 mg/L in stage one, and ≈ 3.7 mg/L in stage 2. Limestone and zeolite were employed as main supporting media to build non-vegetated and vegetated cells with Phragmites australis. The system was very effective in the removal of arsenic and iron (> 96%), and lead (> 94%) throughout the whole experimental period, having the four treatment types a similar performance. The main effect of the media type was on the pH adjustment capacity: limestone cells were able to raise the pH to ≈ 7.1, whereas zeolite cells raised it to ≈ 3.8. The contribution of plant uptake to the overall removal of As, Fe and Zn was minor; accounting for less than 0.02%, 0.07% and 0.7% respectively. As such, pollutants were mainly retained in the wetland beds. Our results suggest that limestone is recommended over zeolite as wetland medium mainly due to its neutralization capacity.

Rational Design of an Iridium-Tungsten Composite with an Iridium-Rich Surface for Acidic Water Oxidation.

Developing highly active and stable water oxidation catalysts with reduced cost in acidic media plays a critical role in clean energy technologies such as fuel cells and electrolyzers. Precious iridium-based oxides are still the only oxygen evolution reaction (OER) catalysts with reasonable activity and stability in acid. Herein, we design iridium-tungsten composites with a metallic tungsten-rich core and an iridium-rich surface by the sol-gel method followed by hydrogen reduction. The thus obtained iridium-tungsten catalyst shows much higher intrinsic water oxidation activity (100 mA/mgIr at an overpotential of 290 mV) and stability (100 h at 10 mA/cm2geom) together with reduced iridium content (33 wt % only) as compared with pure iridium oxide. An operando method using H2O2 as a probe molecule is developed to determine the relative adsorption strength of the reaction intermediates (*OH and *OOH) in the OER process. Detailed characterization shows that the tungsten-incorporated surface not only modulates the adsorption energy of oxygen intermediates on iridium but also enhances the stability of iridium species in acid, while the metallic tungsten core exhibits high electrical conductivity, all of which collectively give rise to the much enhanced catalytic performance of iridium-tungsten composite in acidic water oxidation. A single-membrane electrode assembly is further prepared to demonstrate the advantages and potential application of iridium-tungsten composite in practical proton exchange membrane electrolyzers.

Robust and Stable Acidic Overall Water Splitting on Ir Single Atoms.

Single-atom electrocatalysts (SAEs) can realize the target of low-cost by maximum atomic efficiency. However, they usually suffer performance decay due to high energy states, especially in a harsh acidic water splitting environment. Here, we conceive and realize a double protecting strategy that ensures robust acidic water splitting on Ir SAEs by dispersing Ir atoms in/onto Fe nanoparticles and embedding IrFe nanoparticles into nitrogen-doped carbon nanotubes (Ir-SA@Fe@NCNT). When Ir-SA@Fe@NCNT acts as a bifunctional electrocatalyst at ultralow Ir loading of 1.14 µg cm-2, the required overpotentials to deliver 10 mA cm-2 are 250 and 26 mV for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in 0.5 M H2SO4 electrolyte corresponding to 1370- and 61-fold better mass activities than benchmark IrO2 and Pt/C at an overpotential of 270 mV, respectively, resulting in only 1.51 V to drive overall water splitting. Moreover, remarkable stability is also observed compared to Pt/C-IrO2.

Does dissolved organic carbon from Amazon black water (Brazil) help a native species, the tambaqui Colossoma macropomum to maintain ionic homeostasis in acidic water?

To assess how the quality and properties of the natural dissolved organic carbon (DOC) could drive different effects on gill physiology, we analysed the ionoregulatory responses of a native Amazonian fish species, the tambaqui Colossoma macropomum, to the presence of dissolved organic carbon (DOC; 10 mg l-1 ) at both pH 7.0 and pH 4.0 in ion-poor water. The DOC was isolated from black water from São Gabriel da Cachoeira (SGC) in the upper Rio Negro of the Amazon (Brazil) that earlier been shown to protect a non-native species, zebrafish Danio rerio against low pH under similar conditions. Transepithelial potential (TEP), net flux rates of Na+ , Cl- and ammonia and their concentrations in plasma and Na+ , K+ ATPase; v-type H+ ATPase and carbonic anhydrase activities in gills were measured. The presence of DOC had negligible effects at pH 7.0 apart from lowering the TEP, but it prevented the depolarization of TEP that occurred at pH 4.0 in the absence of DOC. However, contrary to our initial hypothesis, SGC DOC was not protective against the effects of low pH. Colossoma macropomum exposed to SGC DOC at pH 4.0 experienced greater net Na+ and Cl- losses, decreases of Na+ and Cl- concentrations in plasma and elevated plasma ammonia levels and excretion rates, relative to those exposed in the absence of DOC. Species-specific differences and changes in DOC properties during storage are discussed as possible factors influencing the effectiveness of SGC DOC in ameliorating the effects of the acid exposure.

Self-Healing of Polymer in Acidic Water toward Strength Restoration through the Synergistic Effect of Hydrophilic and Hydrophobic Interactions.

To improve reliability, durability, and reworkability of bulk polymers utilized in ubiquitous acidic water, the authors develop a novel hyperbranched polymer capable of self-healing and recycling in a low-pH aqueous environment. The hyperbranched polymer has many hydrophilic and hydrophobic terminal groups. When it is damaged in acidic water, the hydrophilic groups are protonated, forming hydrogen bonds, and closing the crack. Meanwhile, hydrophobic interactions of hydrophobic groups are gradually established across the interface because of the intimate contact of the cracked surface, further reinforcing the rebonded portion. The amphiphilic structure proves to meet both the thermodynamic and kinetic requirements for autonomous rehabilitation. As a result, the unfavored water, which used to impede adhesion between hydrophobic polymeric materials, turns into a positive aid to crack healing. The mechanism involved is carefully analyzed and verified in terms of micro- and macroscopic techniques. The proposed operating environment-oriented design of the stimulus-responsive macromolecule may help to broaden the family of underwater self-healing polymers and their application scope.

Neutralization of acidic drainage by Cryptococcus sp. T1 immobilized in alginate beads.

We isolated Cryptococcus sp. T1 from Lake Tazawa's acidic water in Japan. Cryptococcus sp. T1 neutralized an acidic casamino acid solution (pH 3.0) and released ammonia from the casamino acids to aid the neutralization. The neutralization volume was estimated to be approximately 0.4 mL/h. The casamino acids' amino acids decreased (1.24→0.15 mM); ammonia increased (0.22→0.99 mM). We neutralized acidic drainage water (1 L) from a Tamagawa River neutralization plant, which was run through the column with the T1-immobilized alginate beads at a flow rate of 0.5 mL/min, and observed that the viscosity, particle size and amounts of the alginate beads affected the acidic drainage neutralization with an increase of the pH value from 5.26 to 6.61 in the last fraction. An increase in the Al concentration decreased Cryptococcus sp. T1's neutralization ability. After 48 h, the pH of acidic water with 50 mg/L Al was apparently lower than that without Al. Almost no pH increase was observed at 75 mg/L.