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The local coordination environment around catalytically active sites plays a vital role in tuning the activity of electrocatalysts made of carbon-supported metal nanoparticles. However, the rational design of electrocatalysts with improved performance by controlling this environment is hampered by synthetic limitations and insufficient mechanistic understanding of how the catalytic phase forms. Here we show that introducing F atoms into Pd/N–C catalysts modifies the environment around the Pd and improves both activity and durability for the ethanol oxidation reaction and the oxygen reduction reaction. Our data suggest that F atom introduction creates a more N-rich Pd surface, which is favourable for catalysis. Durability is enhanced by inhibition of Pd migration and decreased carbon corrosion. A direct ethanol fuel cell that uses the Pd/N–C catalyst with F atoms introduced for both the ethanol oxidation reaction and oxygen reduction reaction achieves a maximum power density of 0.57 W cm−2 and more than 5,900 hours of operation. Pd/C catalysts containing other heteroatoms (P, S, B) can also be improved through the addition of F atoms. Metal- and N-coordinated carbon materials are promising electrocatalysts, but improved activity and stability are desirable for fuel cell applications. Chang et al. address this by introducing F atoms into Pd/N–C catalysts, modifying the environment around the Pd and enhancing performance for ethanol oxidation and oxygen reduction.

The ocean is an important inventory of anthropogenic mercury (Hg), yet the history of anthropogenic Hg accumulation in the ocean remains largely unexplored. Deep-sea corals are an emerging archive of past ocean chemistry, which take in sinking or suspended particulate organic matter as their food sources. Such organic matter would exchange Hg with the local seawater before being consumed by the deep, sea corals. As such, the organics preserved in the coral skeleton may record the Hg evolution of the ambient seawater during the time of coral growth. Here, we report the first data on Hg concentrations variability of a deep-sea proteinaceous coral in the oligotrophic North Pacific at the water depth of 1 249 m, in attempt to understand the transfer of anthropogenic Hg into the deep Pacific ocean over the last seven centuries. We find that the Hg concentrations of different coral growth layers have remained relatively constant albeit with considerable short-term variability through time. The overall stable Hg concentration of the last seven centuries recorded in our sample suggests that anthropogenic pollution is not yet a clearly resolvable component in the deep oligotrophic North Pacific waters, in agreement with recent estimation from modelling works and observational studies of modern seawater profiles. As there is hardly an unambiguous way to separate anthropogenic Hg from the natural background based on recent seawater profiles, our historical data provide valuable information helping to understand the oceanic cycle of Hg through time.

Electrochemical reduction of CO2 is a promising route for sustainable production of fuels. A grand challenge is developing low-cost and efficient electrocatalysts that can enable rapid conversion with high product selectivity. Here we design a series of nickel phthalocyanine molecules supported on carbon nanotubes as molecularly dispersed electrocatalysts (MDEs), achieving CO2 reduction performances that are superior to aggregated molecular catalysts in terms of stability, activity and selectivity. The optimized MDE with methoxy group functionalization solves the stability issue of the original nickel phthalocyanine catalyst and catalyses the conversion of CO2 to CO with >99.5% selectivity at high current densities of up to −300 mA cm−2 in a gas diffusion electrode device with stable operation at −150 mA cm−2 for 40 h. The well-defined active sites of MDEs also facilitate the in-depth mechanistic understandings from in situ/operando X-ray absorption spectroscopy and theoretical calculations on structural factors that affect electrocatalytic performance. Widespread deployment of electrochemical CO2 reduction requires low-cost catalysts that perform well at high current densities. Zhang et al. show that methoxy-functionalized nickel phthalocyanine molecules on carbon nanotubes can operate as high-performing molecularly dispersed electrocatalysts at current densities of up to −300 mA cm–2.

Iron (Fe) is a productivity-limiting nutrient in the ocean. However, the sources of dissolved Fe (dFe) in the deep ocean and how they respond to tectonic and climate changes are still poorly understood. In the northern hemisphere, dust flux to the low-latitude western Pacific has increased dramatically since the late Miocene associated with intense aridification of the Asian inland. Meanwhile, the terrigenous material supply to the open ocean might have also changed as a result of the reorganization of the Pacific circulation due to the gradual closure of seaways in the low latitudes. Therefore, the western Pacific is a characteristic region for understanding the sources of dFe in the deep ocean and their responses to long term climate changes. Here, we present data on isotopic evolution of dFe and dissolved Pb since ∼8 Ma based on ferromanganese crust METG-03 (16.0°N, 152.0°E, 3850 m water depth) in the western Pacific deep water. Our results show that δ56Fe of the crust remains fairly stable since the late Miocene, i.e., about −0.32±0.08‰ (2SD). We infer that δ56Fe of dFe in the deep western Pacific is relatively invariant at ∼0.45 ±0.1‰ based on the Fe isotopic fractionation between hydrogenetic crust and the seawater dissolved component. The reconstructed isotope signature is similar to the measured δ56Fe value (0.37±0.15‰) of the intermediate to deep waters in the modern low-latitude western Pacific region close to the island arcs, but is significantly higher than that of the eastern Pacific deep waters near South America which is controlled by the reductive dissolution of continental shelf sediments and the hydrothermal inputs (δ56Fe

Background The radiation-induced lung injury (RILI) in patients with advanced non-small cell lung cancer (NSCLS) is very common in clinical settings; we aimed to evaluate the risk factors of RILI in NSCLS patients, to provide insights into the treatment of NSCLS. Methods NSCLC patients undergoing three-dimensional conformal radiotherapy (3D-CRT) in our hospital from June 1, 2018, to June 30, 2020, were included. The characteristics and treatments of RILI and non-RILI patients were analyzed. Logistic regression analyses were conducted to assess the risk factors of RILI in patients with NSCLC. Results A total of 126 NSCLC patients were included; the incidence of RILI in NSCLC patients was 35.71%. There were significant differences in diabetes, smoke, chronic obstructive pulmonary disease (COPD), concurrent chemotherapy, radiotherapy dose, and planning target volume (PTV) between the RILI group and the non-RILI group (all P < 0.05). Logistic regression analyses indicated that diabetes (OR 3.076, 95%CI 1.442~5.304), smoke (OR 2.745, 95%CI 1.288~4.613), COPD (OR 3.949, 95%CI 1.067~5.733), concurrent chemotherapy (OR 2.072, 95%CI 1.121~3.498), radiotherapy dose ≥ 60 Gy (OR 3.841, 95%CI 1.932~5.362), and PTV ≥ 396 (OR 1.247, 95%CI 1.107~1.746) were the independent risk factors of RILI in patients with NSCLC (all P < 0.05). Conclusions RILI is commonly seen in NSCLS patients; early targeted measures are warranted for patients with those risk factors; future studies with larger sample sizes and different areas are needed to further elucidate the influencing factors of RILI in the treatment of NSCLS.

Platinum group metal (PGM)-free catalysts that are also iron free are highly desirable for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells, as they avoid possible Fenton reactions. Here we report an efficient ORR catalyst that consists of atomically dispersed nitrogen-coordinated single Mn sites on partially graphitic carbon (Mn-N-C). Evidence for the embedding of the atomically dispersed MnN4 moieties within the carbon surface-exposed basal planes was established by X-ray absorption spectroscopy and their dispersion was confirmed by aberration-corrected electron microscopy with atomic resolution. The Mn-N-C catalyst exhibited a half-wave potential of 0.80 V versus the reversible hydrogen electrode, approaching that of Fe-N-C catalysts, along with significantly enhanced stability in acidic media. The encouraging performance of the Mn-N-C catalyst as a PGM-free cathode was demonstrated in fuel cell tests. First-principles calculations further support the MnN4 sites as the origin of the ORR activity via a 4e− pathway in acidic media. Platinum group metal- and iron-free catalysts are highly desirable for the oxygen reduction reaction in proton-exchange membrane fuel cells. Now, Wu and co-workers show a carbon catalyst with atomically dispersed single Mn sites as an efficient catalyst with enhanced stability in acidic media.

Highlights This is the first review paper on the studies of electrocatalysts using advanced in situ X-ray absorption spectroscopy (XAS). This paper reviews the literatures to-date on new applications of in situ XAS (e.g., single-atom catalysts, surface reactions, nanoparticle size, and site occupation) that traditional XAS has not touched. This review focuses mostly on recent publications after 2010., Nanoscale electrocatalysts have exhibited promising activity and stability, improving the kinetics of numerous electrochemical reactions in renewable energy systems such as electrolyzers, fuel cells, and metal-air batteries. Due to the size effect, nano particles with extreme small size have high surface areas, complicated morphology, and various surface terminations, which make them different from their bulk phases and often undergo restructuring during the reactions. These restructured materials are hard to probe by conventional ex-situ characterizations, thus leaving the true reaction centers and/or active sites difficult to determine. Nowadays, in situ techniques, particularly X-ray absorption spectroscopy (XAS), have become an important tool to obtain oxidation states, electronic structure, and local bonding environments, which are critical to investigate the electrocatalysts under real reaction conditions. In this review, we go over the basic principles of XAS and highlight recent applications of in situ XAS in studies of nanoscale electrocatalysts.

Rice black-streaked dwarf disease, caused by the rice black-streaked dwarf virus (RBSDV), can lead to severe yield losses in rice. The deployment of resistant cultivars is an effective disease control measure, but few studies related to the genetics and breeding of RBSDV resistance have been reported in rice. Here, we identified ‘IR36’ (indica) and ‘L5494’ (japonica) as resistant and susceptible parents, respectively, using a field test, and 208 recombinant inbred lines were derived from their cross. A genetic analysis indicated that the resistance of rice materials to RBSDV was controlled by quantitative trait loci (QTLs). A total of 12 QTLs for RBSDV resistance on chromosomes 1, 6, 8 and 9 were identified in three environments (2013–2015), and QTLs in two marker intervals, RM19234–CHR6-2 and RM3700–RM160 on chromosomes 6 and 9, respectively, were consistently detected. These QTLs explained 6.19–29.00 % of the total phenotypic variation for rice black-streaked dwarf disease incidence. The alleles enhancing resistance on chromosomes 6 and 8 originated from ‘IR36’, whereas the alleles on chromosomes 1 and 9 originated from ‘L5494’. The materials and identified resistance QTLs in this study are expected to be useful resources for efficiently breeding rice cultivars resistant to RBSDV.

Restructuring-induced catalytic activity is an intriguing phenomenon of fundamental importance to rational design of high-performance catalyst materials. We study three copper-complex materials for electrocatalytic carbon dioxide reduction. Among them, the copper(II) phthalocyanine exhibits by far the highest activity for yielding methane with a Faradaic efficiency of 66% and a partial current density of 13 mA cm−2 at the potential of – 1.06 V versus the reversible hydrogen electrode. Utilizing in-situ and operando X-ray absorption spectroscopy, we find that under the working conditions copper(II) phthalocyanine undergoes reversible structural and oxidation state changes to form ~ 2 nm metallic copper clusters, which catalyzes the carbon dioxide-to-methane conversion. Density functional calculations rationalize the restructuring behavior and attribute the reversibility to the strong divalent metal ion–ligand coordination in the copper(II) phthalocyanine molecular structure and the small size of the generated copper clusters under the reaction conditions., The catalytic conversion of carbon dioxide into value-added products requires an understanding of the active species present under working conditions. Here, the authors discover copper-containing complexes to reversibly transform during electrocatalysis into methane-producing copper nanoclusters.