Promoting electrocatalytic CO2 reduction to formate via sulfur-boosting water activation on indium surfaces

一般认为，H2O还原析氢反应是CO2还原反应的竞争反应，若促进H2O活化将降低CO2还原反应的法拉第效率。因此，基于该认识设计出的高CO2还原法拉第效率的催化剂常常活性低。王野课题组打破这种认识，提出H2O分子活化在CO2还原中起着重要的作用，成功合成出硫修饰In催化剂来活化H2O分子而促进CO2还原制甲酸的新方法，该催化剂在非常宽的电流密度范围内（25~100 mA cm-2），均可以维持85%以上的甲酸法拉第效率。将硫拓展至硒和碲等其它硫族元素以及将金属铟拓展至铋和锡等其它p区金属，均实现很好的促进效果，表明通过促进水的活化来提高CO2电催化还原性能具有普适性。该工作为理性设计高效的CO2还原电催化剂提供了新策略。 该研究工作实验部分主要由王野、张庆红教授指导，能源材料化学协同创新中心iChEM2016级博士生马文超、固体表面物理化学国家重点实验室高级工程师谢顺吉（共同第一作者）完成；理论计算部分由吴德印教授指导，2015级博士生张霞光（共同第一作者）完成。醇醚酯国家工程实验室高级工程师康金灿参与了部分实验表征。上海光源姜政教授和孙凡飞博士为同步辐射表征提供了支持。【Abstract】Electrocatalytic reduction of CO2 to fuels and chemicals is one of the most attractive routes for CO2 utilization. Current catalysts suffer from low faradaic efficiency of a CO2-reduction product at high current density (or reaction rate). Here, we report that a sulfur-doped indium catalyst exhibits high faradaic efficiency of formate (>85%) in a broad range of current density (25–100 mA cm−2) for electrocatalytic CO2 reduction in aqueous media. The formation rate of formate reaches 1449 μmol h−1 cm−2 with 93% faradaic efficiency, the highest value reported to date. Our studies suggest that sulfur accelerates CO2 reduction by a unique mechanism. Sulfur enhances the activation of water, forming hydrogen species that can readily react with CO2 to produce formate. The promoting effect of chalcogen modifiers can be extended to other metal catalysts. This work offers a simple and useful strategy for designing both active and selective electrocatalysts for CO2This work was supported by the National Key Research and Development Program of the Ministry of Science and Technology of China (No. 2017YFB0602201), the National Natural Science Foundation of China (Nos. 21690082, 91545203, and 21503176). We thank staff at the BL14W1 beamline of the Shanghai Synchrotron Radiation Facilities (SSRF) for assistance with the EXAFS measurements. 研究工作得到科技部重点研发计划（批准号：2017YFB0602201）和国家自然科学基金（批准号：21690082、91545203、21503176）等项目的资助

De Novo Transcriptomic Analysis of an Oleaginous Microalga: Pathway Description and Gene Discovery for Production of Next-Generation Biofuels

Background: Eustigmatos cf. polyphem is a yellow-green unicellular soil microalga belonging to the eustimatophyte with high biomass and considerable production of triacylglycerols (TAGs) for biofuels, which is thus referred to as an oleaginous microalga. The paucity of microalgae genome sequences, however, limits development of gene-based biofuel feedstock optimization studies. Here we describe the sequencing and de novo transcriptome assembly for a non-model microalgae species, E. cf. polyphem, and identify pathways and genes of importance related to biofuel production. Results: We performed the de novo assembly of E. cf. polyphem transcriptome using Illumina paired-end sequencing technology. In a single run, we produced 29,199,432 sequencing reads corresponding to 2.33 Gb total nucleotides. These reads were assembled into 75,632 unigenes with a mean size of 503 bp and an N50 of 663 bp, ranging from 100 bp to.3,000 bp. Assembled unigenes were subjected to BLAST similarity searches and annotated with Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) orthology identifiers. These analyses identified the majority of carbohydrate, fatty acids, TAG and carotenoids biosynthesis and catabolism pathways in E. cf. polyphem. Conclusions: Our data provides the construction of metabolic pathways involved in the biosynthesis and catabolism of carbohydrate, fatty acids, TAG and carotenoids in E. cf. polyphem and provides a foundation for the molecular genetics and functional genomics required to direct metabolic engineering efforts that seek to enhance the quantity and character o

Why Are Outcomes Different for Registry Patients Enrolled Prospectively and Retrospectively? Insights from the Global Anticoagulant Registry in the FIELD-Atrial Fibrillation (GARFIELD-AF).

Background: Retrospective and prospective observational studies are designed to reflect real-world evidence on clinical practice, but can yield conflicting results. The GARFIELD-AF Registry includes both methods of enrolment and allows analysis of differences in patient characteristics and outcomes that may result. Methods and Results: Patients with atrial fibrillation (AF) and ≥1 risk factor for stroke at diagnosis of AF were recruited either retrospectively (n = 5069) or prospectively (n = 5501) from 19 countries and then followed prospectively. The retrospectively enrolled cohort comprised patients with established AF (for a least 6, and up to 24 months before enrolment), who were identified retrospectively (and baseline and partial follow-up data were collected from the emedical records) and then followed prospectively between 0-18 months (such that the total time of follow-up was 24 months; data collection Dec-2009 and Oct-2010). In the prospectively enrolled cohort, patients with newly diagnosed AF (≤6 weeks after diagnosis) were recruited between Mar-2010 and Oct-2011 and were followed for 24 months after enrolment. Differences between the cohorts were observed in clinical characteristics, including type of AF, stroke prevention strategies, and event rates. More patients in the retrospectively identified cohort received vitamin K antagonists (62.1% vs. 53.2%) and fewer received non-vitamin K oral anticoagulants (1.8% vs . 4.2%). All-cause mortality rates per 100 person-years during the prospective follow-up (starting the first study visit up to 1 year) were significantly lower in the retrospective than prospectively identified cohort (3.04 [95% CI 2.51 to 3.67] vs . 4.05 [95% CI 3.53 to 4.63]; p = 0.016). Conclusions: Interpretations of data from registries that aim to evaluate the characteristics and outcomes of patients with AF must take account of differences in registry design and the impact of recall bias and survivorship bias that is incurred with retrospective enrolment. Clinical Trial Registration: - URL: http://www.clinicaltrials.gov . Unique identifier for GARFIELD-AF (NCT01090362)

Summary for the <i>E.</i> cf. <i>polyphem</i> transcriptome.

<p>Summary for the <i>E.</i> cf. <i>polyphem</i> transcriptome.</p

Glycolysis pathway reconstructed based on the <i>de novo</i> assembly and annotation of <i>E.</i> cf. <i>polyphem</i> transcriptome.

<p>Identified enzymes are shown in boxes and include: HK, hexokinase (EC:2.7.1.1); GCK, glucokinase (EC: 2.7.1.2); G6PI, glucose-6-phosphate isomerase (EC: 5.3.1.9); PFK, phosphofructokinase-6 (EC: 2.7.1.11); FBA, fructose-bisphosphate aldolase (EC:4.1.2.13); TPI, triose-phosphate isomerase (EC: 5.3.1.1); GAPDH, glyceraldehyde-3-phosphate dehydrogenase (EC: 1.2.1.9, 1.2.1.12); GPDH, glycerol-3-phosphate dehydrogenase (EC:1.1.1.8); PGK, phosphoglycerate kinase (EC: 2.7.2.3); PGAM, phosphoglycerate mutase (EC: 5.4.2.1); ENO, enolase (EC: 4.2.1.11); PK, pyruvate kinase (EC: 2.7.1.40); PDC, pyruvate decarboxylase (EC: 4.1.1.1); ADH, alcohol dehydrogenase (EC: 1.1.1.1); PDHC, the pyruvate dehydrogenase complex consisting of PDHB, pyruvate dehydrogenase (acetyl-transferring) (EC: 1.2.4.1), DLAT, dihydrolipoamide acetyltransferase (EC: 2.3.1.12), DLD, dihydrolipoyl dehydrogenase (EC: 1.8.1.4). G-6-P, glucose-6-phosphate; F-6-P, fructose 6-phosphate; FBP, fructose-1,6-bisphosphate; GA3P, glyceraldehyde-3-phosphate; DHAP, dihydroxyacetone phosphate; G-3-P, glycerol-3-phosphate; 1,3BPG, 1, 3-bisphosphoglycerate; 3PG, 3-phosphoglycerate; 2PG, 2-phosphoglycerate; PEP, phosphoenolpyruvate.</p

Enzymes involved in chrysolaminarin biosynthesis and metabolism identified by annotation of the <i>E.</i> cf. <i>polyphem</i> transcriptome.

1<p>In cases where multiple transcripts have been aligned with the associated enzymes in the model organisms, average similarity is reported.</p>2<p>NM denotes that the annotated transcripts did not match the sequence of corresponding enzyme in model organisms.</p