C‐Bound or O‐Bound Surface: Which One Boosts Electrocatalytic Urea Synthesis?

Abstract

The electrocatalytic C−N coupling from carbon dioxide and nitrate under ambient conditions is kind of sustainable and promising alternative method for urea synthesis. To date, the influence of catalyst surface properties on molecular adsorption configuration and electrocatalytic urea synthesis activity is unclear. In this work, we proposed that the urea synthesis activity is closely linked with the localized surface charge on bimetallic electrocatalysts, it is found that a negatively charged surface induces C‐bound path and boosts urea synthesis. The urea yield rate can reach 13.1 mmol g−1 h−1 on negatively charged Cu97In3‐C, which is about 13 times that of positively charged Cu30In70‐C counterpart with O‐bound surface. This conclusion also applies to Cu−Bi and Cu−Sn systems. The molecular modification shifts the surface of Cu97In3‐C to positively charged state, which leads to a sharp decline in urea synthesis performance. We demonstrated that the C‐bound surface is more favorable than O‐bound one to boost electrocatalytic urea synthesis.

Emerging Electrocatalysts in Urea Production

“…The second C−N bond is constructed by coupling another * NO 2 with * CO 2 NH 2 (obtained from the hydrogenation of * CO 2 NO 2 ) to form * CO 2 NO 2 NH 2 , followed by the final production of urea after several PCET steps. More importantly, it is also found that the binding configuration of CO 2 has a great influence on urea formation [17] . For example, * COOH with C atom bound on the negatively charged surface is more beneficial for the C−N coupling and urea production than those of * OCHO with O atom bond on the positively charged surface.…”

“…More importantly, it is also found that the binding configuration of CO 2 has a great influence on urea formation. [17] For example, *COOH with C atom bound on the negatively charged surface is more beneficial for the CÀ N coupling and urea production than those of *OCHO with O atom bond on the positively charged surface. In addition, NO 2 À is also used as N feedstock to synthesize urea.…”

“…[24] As an example, Feng et al synthesized Te-doped Pd materials, where Te atoms can optimize the adsorption of CO 2 / CO, and decrease the energy barrier for CÀ N coupling (*CONH 2 ) to enhance urea generation. [18] Moreover, Liu et al prepared a series of CuIn alloys (supported on the carbon black) with different atom ratios and they found that Cu 97 In 3 À C with a negatively charged surface exhibits the best urea yield rate of 13.1 mmol g À 1 h À 1 (Figure 4e) in the co-reduction of CO 2 and NO 3 À , compared with Cu 30 In 70 À C, CuÀ C or InÀ C. [17] To elucidate the importance of the charged state on the alloy surface, the 4- À 1 at À 0.4 V vs. RHE. [10c] In addition, Lee et al prepared self-assembled AuCu alloy nanofibers as electrocatalysts for urea production from the co-reduction of CO 2 and NO 2…”

Non‐Linear Kinetics of The Lithium Metal Anode on Li6PS5Cl at High Current Density: Dendrite Growth and the Role of Lithium Microstructure on Creep

“…It will be highly interesting to study the influence of a modified SEI with different conductivity on the observed non-linear kinetics in the future. SEI modification aiming for improved anode stability is increasingly being studied, [45,46] however, we are not aware of any systematic study yet. We expect that the observed non-linear behavior will strongly depend on the type of SEI.…”

Coactivation of Multiphase Reactants for the Electrosynthesis of Urea

“…By contrast, electrocatalytic technology to reduce N 2 and CO 2 to urea is a mild and efficient technology to turn waste into treasure. [13][14][15][16][17][18][19][20][21][22][23][24][25] Zhang and coworkers [26] prepared a heterostructures catalyst to promote the adsorption of noble gases by designing a space charge region; Li and co-workers [27] investigated the ability of 2D metal borides to electrosynthesize urea under ambient conditions and promote urea production by inhibiting the side reaction of N 2 reduction to NH 3 . Wang and co-workers [28] designed a PdCu nanoparticle grown on titanium dioxide to form C-N bond through thermodynamic spontaneous coupling between *N=N* and *CO.…”