A high performance non-noble metal electrocatalyst for the oxygen reduction reaction derived from a metal organic framework

The development of a non-precious metal electrocatalyst （NPME） with a performance superior to commercial Pt/C for the oxygen reduction reaction （ORR） is important for the commercialization of fuel cells. We report the synthesis of a NPME by heat-treating Co-based metal organic frameworks （ZIF-67） with a small average size of 44 nm. The electrocatalyst pyrolyzed at 600 ~C showed the best performance and the performance was enhanced when it was supported on BP 2000. The resulting electrocatalyst was composed of 10 nm Co nanoparticles coated by 3-12 layers of N doped graphite layers which as a whole was embedded in a carbon matrix. The ORR performance of the electrocatalyst was tested by rotating disk electrode tests in O2-saturated 0.1 mol/L KOH under ambient conditions. The electrocatalyst （1.0 mg/cm~] showed an onset potential of 1.017 V （[vs. RHE] and a half-wave potential of 0.857 V （vs. RHE], which showed it was as good as the commer- cial Pt/C （20 BgPt/cm2）. Furthermore, the electrocatalyst possessed much better stability and re- sistance to methanol crossover than Pt/C.

REDUCTION BY HYPOPHOSPHOROUS ACID IN ORGANIC SYNTHESIS

Hypophosphorous acid and its salt were found to serve as a new agent for selective reduction of α,β-unsaturated carbonyl compounds under mild reaction conditions.

Recent progress in cathodic reduction-enabled organic electrosynthesis: Trends, challenges, and opportunities

Compared with general redox chemistry,electrochemistry using the electron as a potent,controllable,yet traceless alternative to chemical oxidants/reductants usually offers more sustainable options for achieving selective organic synthesis.With its environmentally benign features gradually being uncovered and studied,organic electrosynthesis is currently undergoing a revival and becoming a rapidly growing area within the synthetic community.Among the electrochemical transformations,the anodically enabled ones have been far more extensively exploited than those driven by cathodic reduction,although both approaches are conceptually attractive.To stimulate the development of cathodically enabled organic reactions,this review summarizes the recently developed reductive electrosynthetic protocols,discussing and highlighting reaction features,substrate scopes,applications,and plausible mechanisms to reveal the recent trends in this area.Herein,cathodic reduction-enabled preparative organic transformations are categorized into four types:reduction of(1)unsaturated hydrocarbons,(2)heteroatom-containing carbon-based unsaturated systems,(3)saturated C-hetero or C–C polar/strained bonds,and(4)hetero-hetero linkages.Apart from net electroreductive reactions,a few examples of reductive photo-electrosynthesis as well as paired electrolysis are also introduced,which offer opportunities to overcome certain limitations and improve synthetic versatility.The electrochemically driven,transition metal-catalyzed reductive cross-couplings that have been comprehensively discussed in several other recent reviews are not included here.

Sunlight-driven reduction of silver ion to silver nanoparticle by organic matter mitigates the acute toxicity of silver to Daphnia magna

Due to the unique antibacterial activities, silver nanoparticles（AgNPs） have been extensively used in commercial products. Anthropogenic activities have released considerable AgNPs as well as highly toxic silver ion（Ag^＋） into the aquatic environment.Our recent study revealed that ubiquitous natural organic matter（NOM） could reduce Ag^＋to Ag NP under natural sunlight. However, the toxic effect of this process is not well understood. In this work, we prepared mixture solution of Ag^＋and AgNPs with varied Ag^＋% through the sunlight-driven reduction of Ag^＋by NOM and investigated the acute toxicity of the solutions on Daphnia magna. Formation of AgNPs was demonstrated and characterized by comprehensive techniques and the fraction of unconverted Ag^＋was determined by ultrafiltration-inductively coupled plasma mass spectrometry determination. The formation of AgNPs enhanced significantly with the increasing of solution p H and cumulative photosynthetically active radiation of sunlight. The toxicity of the resulting solution was further investigated by using freshwater crustacean D. magna as a model and an 8 hr-median lethal concentration（LC50） demonstrated that the reduction of Ag^＋by NOM to AgNPs significantly mitigated the acute toxicity of silver. These results highlight the importance of sunlight and NOM in the fate, transformation and toxicity of Ag^＋and AgNPs,and further indicate that the acute toxicity of AgNPs should be mainly ascribed to the dissolved Ag^＋from AgNPs.

Cr(Ⅵ) reduction capability of humic acid extracted from the organic component of municipal solid waste

The capacity of humic acid extracted from organic waste （HAw） to reduce Cr（Ⅵ） was tested at pH 2.5,4 and 6 and compared with coal-derived humic acid （HAc）.HAw was more effective than HAc in reducing Cr（Ⅵ）.The kinetics of Cr（Ⅵ） reductions depended strongly on pH.The calculation of the apparent rate coefficients indicated that HAw was more efficient at reducing Cr（Ⅵ） than HAc,but was also more efficient than HAs from soil and peat.The reduction capability of HAs depends on the type of functional groups （i.e.,thiols and phenols） present,rather than the free radicals.HAw was more efficient at reducing Cr（Ⅵ） than HAc because more reactive phenols were present,i.e.,methoxy-and methyl-phenols.

Recent advances in nature-inspired nanocatalytic reduction of organic molecules with water

Nature has provided us the assurance and inspiration for thousands of years in synthesizing value-added chemicals,with the assistance of reactive hydrogen species,and water as the ultimate hydrogen source.However,the natural photosynthesis is inefficient due to some intrinsic properties,urging people not only to learn from but also surpass during nature imitation.In this review,we summarized recent progresses on reactive hydrogen species-assisted nanocatalytic reduction of organic molecules towards value-added fine chemicals and pharmaceuticals,with water as the hydrogen source,and especially highlighted how photocatalytically or electrocatalytically evolved reactive hydrogen species synergize with biocatalytic centers and nanocatalytic sites for reduction of organic molecules.The design principles of collaborative semi-artificial systems and nanocatalytic artificial systems,the structure tuning of catalysts for the evolution and utilization of hydrogen species,and the determination of reactive hydrogen species for mechanistic insights were discussed in detail.Finally,perspectives were provided for further advancing this emerging area of nanocatalytic reduction of organic molecules from water(or proton)and organics.