Chlorine evolution reaction has been applied in the production since a century ago. After times of evolution, it has been widely realized by the electrocatalytic process on anode nowadays. However, the anode applied in production contains a large amount of precious metal, increasing the cost. It is thus an opportunity to apply sub-nano catalysts in this field. By regulating the tip effect (TE) of the catalyst, it was discovered that the oxidized sub-nano iridium clusters supported by titanium carbide exhibit much higher efficiency than the single-atom one, which demonstrates the significance of modifying the electronic interaction. Moreover, it exhibits a � 20 % decrease of the electricity, � 98 % selectivity towards chlorine evolution reaction, and high durability of over 350 h. Therefore, this cluster catalyst performs great potential in applying in the practical production and the comprehension of the tip effect on different types of catalysts is also pushed to a higher level.Chlor-alkali production plays a main role in supplying daily chemicals both in life and industry, such as disinfector, chlorine and so on. [1,2] It is one of the stanchions in the world of chemistry. The energy consumption of chlor-alkali has reached � 150 TW h y À 1 , accounting for the 4 % of the electricity generating all over the world. [3] In the process of chlorine production, the electrocatalysis takes charge of 60 % electricity consumption, which indicates that the efficiency of chlorine production is affected by the catalytic performance of chlorine evolution reaction (CER) on anode. [4][5][6][7][8][9][10] At first, the anode applied in CER was firstly the graphite rod, which is of very low cost but with low catalytic selectivity and durability. [11] After many times of evolution, Beer et al. put forward the dimensionally stable anodes (DSA) and the Stucki et al. come up with the anode of IrO 2 / [

Carbonyl and amine are yin and yang in organocatalysis that mutually activate and transform each other. As intrinsically reacting partners, carbonyl and amine tend to condensate, depleting their individual activity when employed as catalysts. Though widely established as prominent catalytic strategies, aminocatalysis and carbonyl catalysis seems not coexist well and a cooperative amine/carbonyl dual catalysis remains virtually unknown. Here we report a cooperative primary amine and ketone dual catalysis in the asymmetric αhydroxylation with H2O2. Besides participating in the typical enamine catalytic cycle, the chiral primary amine catalyst was found to work cooperatively with a ketone catalyst to activate H2O2 via an oxaziridine intermediate derived from in-situ generated ketimine intermediate. The resulted enamine-oxaziridine coupling then facilitated highly-controlled hydroxylation of β-ketocarbonyls that are not possible with other catalytic methods. The dual catalytic approach allows for highly enantioselective α-hydroxylation of a broad range of β-ketocarbonyls. Particularly, late-stage hydroxylation for peptidyl amide or chiral esters can also 2 be achieved with high stereoselectivity. With its operational simplicity and mild conditions, this cooperative amine/ketone catalysis provides a new strategy in catalytic activation of H2O2 and expands the domain of typical amine and carbonyl catalysis to include those challenging transformations.

It is still of great difficulty to develop the non‐platinum catalyst with high catalytic efficiency towards hydrogen evolution reaction via the strategies till now. Therefore, it is necessary to develop the new methods of catalyst designing. Here, we put forward the catalyst designed by the electronic metal–support interaction (EMSI), which is demonstrated to be a reliable strategy to find out the high‐efficiency catalyst. We carried out the density functional theory calculation first to design the proper EMSI of the catalyst. We applied the model of M1‐M2‐X (X=C, N, O) during the calculation. Among the catalysts we chose, the EMSI of Rh1TiC, with the active sites of Rh1‐Ti2C2, is found to be the most proper one for HER. The electrochemical experiment further demonstrated the feasibility of the EMSI strategy. The single atomic site catalyst of Rh1‐TiC exhibits higher catalytic efficiency than that of state‐of‐art Pt/C. It achieves a small overpotential of 22 mV and 86 mV at the at the current density of 10 mA cm−2 and 100 mA cm−2 in acid media, with a Tafel slope of 25 mV dec−1 and a mass activity of 54403.9 mA cm−2 mgRh−1 (vs. 192.2 mA cm−2 mgPt−1 of Pt/C). Besides, it also shows appealing advantage in energy saving compared with Pt/C (≈20 % electricity consuming decrease at 2 kA m−2) Therefore, we believe that the strategy of regulating EMSI can act as a possible way for achieving the high catalytic efficiency on the next step of SACs.

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Chlorine evolution reaction has been applied in the production since a century ago. After times of evolution, it has been widely realized by the electrocatalytic process on anode nowadays. However, the anode applied in production contains a large amount of precious metal, increasing the cost. It is thus an opportunity to apply sub-nano catalysts in this field. By regulating the tip effect (TE) of the catalyst, it was discovered that the oxidized sub-nano iridium clusters supported by titanium carbide exhibit much higher efficiency than the single-atom one, which demonstrates the significance of modifying the electronic interaction. Moreover, it exhibits a � 20 % decrease of the electricity, � 98 % selectivity towards chlorine evolution reaction, and high durability of over 350 h. Therefore, this cluster catalyst performs great potential in applying in the practical production and the comprehension of the tip effect on different types of catalysts is also pushed to a higher level.Chlor-alkali production plays a main role in supplying daily chemicals both in life and industry, such as disinfector, chlorine and so on. [1,2] It is one of the stanchions in the world of chemistry. The energy consumption of chlor-alkali has reached � 150 TW h y À 1 , accounting for the 4 % of the electricity generating all over the world. [3] In the process of chlorine production, the electrocatalysis takes charge of 60 % electricity consumption, which indicates that the efficiency of chlorine production is affected by the catalytic performance of chlorine evolution reaction (CER) on anode. [4][5][6][7][8][9][10] At first, the anode applied in CER was firstly the graphite rod, which is of very low cost but with low catalytic selectivity and durability. [11] After many times of evolution, Beer et al. put forward the dimensionally stable anodes (DSA) and the Stucki et al. come up with the anode of IrO 2 / [