Ru-Cu Nanoheterostructures for Efficient Hydrogen Evolution Reaction in Alkaline Water Electrolyzers.

Combining multiple species working in tandem for different hydrogen evolution reaction (HER) steps is an effective strategy to design HER electrocatalysts. Here, we engineered a hierarchical electrode for the HER composed of amorphous-TiO2/Cu nanorods (NRs) decorated with cost-effective Ru-Cu nanoheterostructures (Ru mass loading = 52 µg/cm2). Such an electrode exhibits a stable, over 250 h, low overpotential of 74 mV at -200 mA/cm2 for the HER in 1 M NaOH. The high activity of the electrode is attributed, by structural analysis, operando X-ray absorption spectroscopy, and first-principles simulations, to synergistic functionalities: (1) mechanically robust, vertically aligned Cu NRs with high electrical conductivity and porosity provide fast charge and gas transfer channels; (2) the Ru electronic structure, regulated by the size of Cu clusters at the surface, facilitates the water dissociation (Volmer step); (3) the Cu clusters grown atop Ru exhibit a close-to-zero Gibbs free energy of the hydrogen adsorption, promoting fast Heyrovsky/Tafel steps. An alkaline electrolyzer (AEL) coupling the proposed cathode and a stainless-steel anode can stably operate in both continuous (1 A/cm2 for over 200 h) and intermittent modes (accelerated stress tests). A techno-economic analysis predicts the minimal overall hydrogen production cost of US$2.12/kg in a 1 MW AEL plant of 30 year lifetime based on our AEL single cell, hitting the worldwide targets (US$2-2.5/kgH2).

High-performance alkaline water electrolyzers based on Ru-perturbed Cu nanoplatelets cathode.

Alkaline electrolyzers generally produce hydrogen at current densities below 0.5 A/cm2. Here, we design a cost-effective and robust cathode, consisting of electrodeposited Ru nanoparticles (mass loading ~ 53 µg/cm2) on vertically oriented Cu nanoplatelet arrays grown on metallic meshes. Such cathode is coupled with an anode based on stacked stainless steel meshes, which outperform NiFe hydroxide catalysts. Our electrolyzers exhibit current densities as high as 1 A/cm2 at 1.69 V and 3.6 A/cm2 at 2 V, reaching the performances of proton-exchange membrane electrolyzers. Also, our electrolyzers stably operate in continuous (1 A/cm2 for over 300 h) and intermittent modes. A total production cost of US$2.09/kgH2 is foreseen for a 1 MW plant (30-year lifetime) based on the proposed electrode technology, meeting the worldwide targets (US$2-2.5/kgH2). Hence, the use of a small amount of Ru in cathodes (~0.04 gRu per kW) is a promising strategy to solve the dichotomy between the capital and operational expenditures of conventional alkaline electrolyzers for high-throughput operation, while facing the scarcity issues of Pt-group metals.

Colloidal Synthesis of Nickel Arsenide Nanocrystals for Electrochemical Water Splitting.

We report a detailed study on the first colloidal synthesis of NiAs nanocrystals. By optimizing the synthesis parameters, we were able to obtain trioctylphosphine-capped NiAs nanoplatelets with an average diameter of ∼10 nm and a thickness of ca. 4 nm. We then studied the performance of such NiAs nanocrystals as electrocatalysts for electrochemical water splitting reactions, namely, acidic hydrogen evolution reaction (HER) and alkaline oxygen evolution reaction (OER). These nanocrystals were found to be the most HER active ones among the transition metal arsenides reported to date despite exhibiting less than 40 h of stability under benchmark operative conditions (i.e., -10 mA cmgeo -2). When tested as alkaline OER electrocatalysts, our NiAs nanocrystals behaved as a pre-catalyst and transformed superficially into an active Ni-oxy/hydroxide. As a result, NiAs nanocrystals featured an OER activity higher than that of benchmark Ni0 nanocrystals. Noticeably, the OER performance, in terms of , was retained for up to 60 h of continuous operation. The present study highlights how transition metal arsenides, whose structural features could be successfully controlled through a proper tuning of the synthetic parameters, might represent an emerging class of materials for electrocatalytic applications.

High-current density alkaline electrolyzers: The role of Nafion binder content in the catalyst coatings and techno-economic analysis.

We report high-current density operating alkaline (water) electrolyzers (AELs) based on platinum on Vulcan (Pt/C) cathodes and stainless-steel anodes. By optimizing the binder (Nafion ionomer) and Pt mass loading (mPt) content in the catalysts coating at the cathode side, the AEL can operate at the following (current density, voltage, energy efficiency -based on the hydrogen higher heating value-) conditions (1.0 A cm-2, 1.68 V, 87.8%) (2.0 A cm-2, 1.85 V, 79.9%) (7.0 A cm-2, 2.38 V, 62.3%). The optimal amount of binder content (25 wt%) also ensures stable AEL performances, as proved through dedicated intermittent (ON-OFF) accelerated stress tests and continuous operation at 1 A cm-2, for which a nearly zero average voltage increase rate was measured over 335 h. The designed AELs can therefore reach proton-exchange membrane electrolyzer-like performance, without relying on the use of scarce anode catalysts, namely, iridium. Contrary to common opinions, our preliminary techno-economic analysis shows that the Pt/C cathode-enabled high-current density operation of single cell AELs can also reduce substantially the impact of capital expenditures (CAPEX) on the overall cost of the green hydrogen, leading CAPEX to operating expenses (OPEX) cost ratio <10% for single cell current densities ≥0.8 A cm-2. Thus, we estimate a hydrogen production cost as low as $2.06 kgH2 -1 for a 30 years-lifetime 1 MW-scale AEL plant using Pt/C cathodes with mPt of 150 µg cm-2 and operating at single cell current densities of 0.6-0.8 A cm-2. Thus, Pt/C cathodes enable the realization of AELs that can efficiently operate at high current densities, leading to low OPEX while even benefiting the CAPEX due to their superior plant compactness compared to traditional AELs.

Tuning the sorption ability of hydroxyapatite/carbon composites for the simultaneous remediation of wastewaters containing organic-inorganic pollutants.

In this paper, we report on the rational design, synthesis, characterization, and application of eco-friendly hydroxyapatite/carbon (HAP/C) composites as effective sorbents for the simultaneous remediation of organic-inorganic pollution in wastewaters. Carbon content in composites ranged from ca. 4 to ca. 20 wt%. Structural and morphological features of the composites were studied by N2 adsorption/desorption analyses, electron microscopy (TEM and HAADF-STEM/EDX) and X-ray powder diffraction (XRPD). These features were correlated with the composition and the exposure of surface functional groups. Surface acid-base groups were assessed by liquid-solid acid/base titrations and results depended on the composition ratio of the two components. Batch adsorption tests, performed with various initial concentrations of pollutant species and dosages, proved that composites merged the sorption properties of the two moieties, being able to simultaneously adsorb organic (methylene blue) and inorganic (Cu(II) and Ni(II)) pollutants. On the optimal carbonaceous scaffold content (ca. 8 wt% carbon), kinetic tests revealed that this composite could almost completely remove high concentrations of co-present pollutants, namely, Cu(II), Ni(II), (300 ppm) and methylene blue (250 ppm) in ca. 1 h, with sorbent dosage of 10 g L-1. In addition, leaching tests proved the permanent retention of the hazardous species on the composites.

Designing "Safer Water." A Virtual Reality Tool for the Safety and the Psychological Well-Being of Citizens Exposed to the Risk of Natural Disasters.

Virtual Reality (VR) is a popular technology to recreate reality-like scenarios, including dangerous ones, in a realistic but safe way. Because of this potential, VR based research has been applied in psychology studies to provide training and education about how to behave in emergencies such as fires, earthquakes, floods, or typhoons. All these different virtual scenarios have been built to observe how people react to emergencies, what behaviors they adopted, what level of stress is generated, and finally, how to increase citizens' safety. However, there is still little research that shows how Virtual Environment (VE) should be designed to convey appropriate social and psychological "cues" to participants. In this work, we present the result of a series of co-design sessions aiming to bring experts to collaborate in setting up virtual scenarios to increase the quality of life, safety perception, and risk awareness in people living in the proximity of a river. Floods are one of the most threatening climate events, and because of climate change, they are expected to become even more frequent. These disasters have a devastating impact on communities, increasing anxiety and stress levels in citizens living close to rivers. We involved relevant stakeholders to design "Safer Water," an immersive, interactive, virtual experience to support citizens in psychologically and behaviorally managing pre and post riverbank breakdown situations. HCI experts, hydrogeological and hydraulic engineers, psychologists, and VEs designers took part in affinity diagram and brainstorming activities. Results show how the adopted method was able to generate suitable virtual scenarios, to highlight and classify relevant design requirements, and to find strategies that could improve the quality of life and psychological well-being in "risk-exposed citizens." The discussion includes a set of open-access guidelines derived from the co-design activities, to support the design of VE for the purposes discussed in the paper.

Capturing and communicating impact of citizen science for policy: A storytelling approach.

In response to the need for approaches to understand how citizen science is currently influencing environmental policy and associated decision making, we devised the Citizen Science Impact StoryTelling Approach (CSISTA). We iteratively designed instruments to be used as tools primarily for citizen science practitioners seeking to understand or communicate policy impacts. We then trialled the CSISTA and associated instruments on four exemplary citizen science initiatives, using different forms of inquiry and collaboration with respective initiative leaders. In this paper, we present CSISTA, with details of the steps for implementing inquiry and storytelling instruments. Additionally, we reflect on insights gained and challenges encountered implementing the approach. Overall, we found the versatility and structure of CSISTA as a process with multiple guiding instruments useful. We envision the approach being helpful, particularly with regards to: 1) gaining an understanding of a citizen science initiative's policy and decision-making impacts; 2) creating short policy impact stories to communicate such impacts to broader audiences; or 3) fulfilling both goals to understand and communicate policy impacts with a unified approach. We encourage others to explore, adapt, and improve the approach. Additionally, we hope that explorations of CSISTA will foster broader discussions on how to understand and strengthen interactions between citizen science practitioners, policy makers, and decision makers at large, whether at local, national, or international scales.

Metal-Support Cooperative Effects in Au/VPO for the Aerobic Oxidation of Benzyl Alcohol to Benzyl Benzoate.

This paper studies the cooperative effect of Au nanoparticles deposited on vanadyl pyrophosphate oxide (VPO) in the liquid phase oxidation of benzyl alcohol. VPO was prepared using the classical method by thermally treating VOHPO4·0.5H2O precursor in reacting atmosphere at 420 °C for a period of 72 h. Au nanoparticles were deposited by incipient wetness method. The catalysts were characterized by means of XRD, TEM, XPS and Raman. The bulk VPO catalyst contains vanadyl pyrophosphate phase ((VO)2P2O7), and a small amount of VOPO4. The catalytic system exhibits a high activity in the base-free liquid phase oxidation of alcohols compared to Au on activated carbon, classic catalyst used for this type of reaction. Au/VPO showed a high peculiar selectivity to benzyl benzoate (76%), an important product used in the pharmaceutical and perfume industries. This behavior might be ascribed to the presence of strong acid sites of VPO, as determined by liquid phase titration. Stability tests performed on Au/VPO showed a deactivation of 10% after the first run, but a constant conversion along the following five cycles. This phenomenon can be attributed to the increase of mean Au particle size (from 19.1 to 23.4 nm) after recycling tests as well as the partial leaching of Au and V in the reaction media. Moreover, XRD evidenced a modification in the VPO structure with the partial formation of VOHPO4·0.5H2O phase.