The
electrocatalytic C–N coupling for one-step urea synthesis
under ambient conditions serves as the promising alternative to the
traditional urea synthetic protocol. However, the hydrogenation of
intermediate species hinders the efficient urea synthesis. Herein,
the oxygen vacancy-enriched CeO2 was demonstrated as the
efficient electrocatalyst with the stabilization of the crucial intermediate
of *NO via inserting into vacant sites, which is
conducive to the subsequent C–N coupling process rather than
protonation, whereas the poor selectivity of C–N coupling with
protonation was observed on the vacancy-deficient catalyst. The oxygen
vacancy-mediated selective C–N coupling was distinguished and
validated by the in situ sum frequency generation
spectroscopy. The introduction of oxygen vacancies tailors the common
catalyst carrier into an efficient electrocatalyst with a high urea
yield rate of 943.6 mg h–1 g–1, superior than that of partial noble-metal-based electrocatalysts.
This work provides novel insights into the catalyst design and developments
of coupling systems.
Co-based spinel oxides,which are of mixing valences with the presence of both Co 2+ and Co 3+ at different atom locations,are considered as promising catalysts for the electrochemical oxidation of 5-hydroxymethylfurfural (HMF). Identifying the role of each atom site in the electroxidation of HMF is critical to design the advanced electrocatalysts.Inthis work, we found that Co 2+ Td in Co 3 O 4 is capable of chemical adsorption for acidic organic molecules,a nd Co 3+ Oh play ad ecisive role in HMF oxidation. Thereafter,t he Cu 2+ was introduced in spinel oxides to enhance the exposure degree of Co 3+ and to boost acidic adsorption and thus to enhance the electrocatalytic activity for HMF electrooxidation significantly.
Electrocatalytic urea synthesis emerged as the promising alternative of Haber–Bosch process and industrial urea synthetic protocol. Here, we report that a diatomic catalyst with bonded Fe–Ni pairs can significantly improve the efficiency of electrochemical urea synthesis. Compared with isolated diatomic and single-atom catalysts, the bonded Fe–Ni pairs act as the efficient sites for coordinated adsorption and activation of multiple reactants, enhancing the crucial C–N coupling thermodynamically and kinetically. The performance for urea synthesis up to an order of magnitude higher than those of single-atom and isolated diatomic electrocatalysts, a high urea yield rate of 20.2 mmol h−1 g−1 with corresponding Faradaic efficiency of 17.8% has been successfully achieved. A total Faradaic efficiency of about 100% for the formation of value-added urea, CO, and NH3 was realized. This work presents an insight into synergistic catalysis towards sustainable urea synthesis via identifying and tailoring the atomic site configurations.
The industrial urea synthesis consists of two consecutive processes, nitrogen + hydrogen → ammonia followed by ammonia + carbon dioxide → urea. The electrocatalytic coupling of carbon source (carbon dioxide) and nitrogen source (nitrogen, nitrite, nitrate) by skipping the ammonia synthetic process might be a promising alternative to achieve the efficient urea synthesis; in this case, two industrial steps with high energy consumption and high pollution are optimized into one renewable energy‐driving electrocatalytic process. Herein, the progress of green urea synthesis is summarized, focusing on the electrocatalytic coupling of carbon source and nitrogen source for direct urea synthesis under ambient conditions. The mechanism researches for urea synthesis are also reviewed, and the future development directions of electrocatalytic urea synthesis are prospected. The electrocatalytic C–N coupling reaction realizes the efficient resource utilization and provides guidance and reference for molecular coupling reactions.
NO is ah armful pollutant to the environment. The traditional removal of NO is hindered by the harsh operating conditions and sacrifice of value-added chemicals.E fficient electrocatalytic oxidation of NO was achieved over plasmatreated commercial carbon cloth, serving as apromising anode substitution reaction to couple with the hydrogen evolution reaction without consumption of hydrogen-containing resources.The introduction of carboxyl groups onto the carbon cloth boosted the electrocatalytic activity via the enhancement of NO chemisorption. Only potentials of 1.39 Va nd 1.07 Vw ere applied to reach the current density of 10 mA cm À2 in neutral and acidic conditions,r espectively,w hichi ss uperior to the state-of-the-art electrocatalysts for oxygen evolution. Energy and environmental concerns on fossil-fuel-derived hydrogen production, ammonia manufacture and nitrate synthesis,a re greatly alleviated. This work provides an original strategy to realizet he resource utilization of NO,t he sustainable nitrate synthesis and hydrogen production in agreen and economical way.
It has been previously shown that (never in mitosis gene A)‐related kinase 2 (NEK2) is upregulated in multiple myeloma (MM) and contributes to drug resistance. However, the mechanisms behind this upregulation remain poorly understood. In this study, it is found that amplification of NEK2 and hypermethylation of distal CpG islands in its promoter correlate strongly with increased NEK2 expression. Patients with NEK2 amplification have a poor rate of survival and often exhibit TP53 deletion, which is an independent prognostic factor in MM. This combination of TP53 knockout and NEK2 overexpression induces asymmetric mitosis, proliferation, drug resistance, and tumorigenic behaviors in MM in vitro and in vivo. In contrast, delivery of wild type p53 and suppression of NEK2 in TP53−/− MM cell lines inhibit tumor formation and enhance the effect of Bortezomib against MM. It is also discovered that inactivating p53 elevates NEK2 expression genetically by inducing NEK2 amplification, transcriptionally by increased activity of cell cycle‐related genes like E2F8 and epigenetically by upregulating DNA methyltransferases. Dual defects of TP53 and NEK2 may define patients with the poorest outcomes in MM with p53 inactivation, and NEK2 may serve as a novel therapeutic target in aggressive MM with p53 abnormalities.
Co-based spinel oxides,which are of mixing valences with the presence of both Co 2+ and Co 3+ at different atom locations,are considered as promising catalysts for the electrochemical oxidation of 5-hydroxymethylfurfural (HMF). Identifying the role of each atom site in the electroxidation of HMF is critical to design the advanced electrocatalysts.Inthis work, we found that Co 2+ Td in Co 3 O 4 is capable of chemical adsorption for acidic organic molecules,a nd Co 3+ Oh play ad ecisive role in HMF oxidation. Thereafter,t he Cu 2+ was introduced in spinel oxides to enhance the exposure degree of Co 3+ and to boost acidic adsorption and thus to enhance the electrocatalytic activity for HMF electrooxidation significantly.
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