Developing efficient catalysts for nitrogen fixation is becoming increasingly important but is still challenging due to the lack of robust design criteria for tackling the activity and selectivity problems, especially for electrochemical nitrogen reduction reaction (NRR). Herein, by means of large-scale density functional theory (DFT) computations, we reported a descriptor-based design principle to explore the large composition space of two-dimensional (2D) biatom catalysts (BACs), namely, metal dimers supported on 2D expanded phthalocyanine (M2-Pc or MM′-Pc), toward the NRR at the acid conditions. We sampled both homonuclear (M2-Pc) and heteronuclear (MM′-Pc) BACs and constructed the activity map of BACs by using N2H* adsorption energy as the activity descriptor, which reduces the number of promising catalyst candidates from over 900 to less than 100. This strategy allowed us to readily identify 3 homonuclear and 28 heteronuclear BACs, which could break the metal-based activity benchmark toward the efficient NRR. Particularly, using the free energy difference of H* and N2H* as a selectivity descriptor, we screened out five systems, including Ti2-Pc, V2-Pc, TiV-Pc, VCr-Pc, and VTa-Pc, which exhibit a strong capability of suppressing the competitive hydrogen evolution reaction (HER) with favorable limiting potential of −0.75, −0.39, −0.74, −0.85, and −0.47 V, respectively. This work not only broadens the possibility of discovering more efficient BACs toward N2 fixation but also provides a feasible strategy for rational design of NRR electrocatalysts and helps pave the way to fast screening and design of efficient BACs for the NRR and other electrochemical reactions.

On-site production of hydrogen peroxide (H2O2) using electrochemical methods could be more efficient than the current industrial process. However, due to the existence of scaling relations for the adsorption of reaction intermediates, there is a long established trade-off between the activity and selectivity of the catalysts, as the enhancement of catalytic activity is typically accompanied by a four-electron O2 reduction reaction (ORR), leading to the reduced selectivity for the H2O2 production. Herein, by means of density functional theory (DFT) computations, we reported the feasibility of several classes of important and representative experimentally achievable single-atom catalysts (SACs) toward two-electron ORR, paying attention to their stability, selectivity, and activity at the acidic medium. Starting from 210 two-dimensional (2D) SACs, we demonstrated that 31 SACs have the potential to break the metal-based scaling relations and simultaneously achieve high activity and selectivity toward H2O2 production and screened out 7 SACs with higher activity than the PtHg4 in acidic media. Especially, a noble metal-free SAC, namely, a single Zn atom centered phthalocyanine (Zn@Pc-N4), has a remarkable activity improvement with a small overpotential of 0.15 V. Moreover, using multivariable analysis and machine-learning techniques, we provided a comprehensive understanding of the underlying origin of the selectivity and activity of SACs and unveiled the intrinsic correlations between structure and catalytic performance. This work may pave a way to the design and discovery of more promising materials for H2O2 production.

To achieve efficient ammonia synthesis via electrochemical nitrogen reduction reaction (NRR), a qualified catalyst should have both high specific activity and large active surface area. However, integrating these two merits into one single material remains a big challenge due to the difficulty in balancing multiple reaction intermediates. Here, it is demonstrated that the boron‐analogues of MXenes, namely “MBenes”, could cope with the challenge and achieve the high activity and large reaction region simultaneously toward NRR. Using extensive density functional theory computations and taking 16 MBenes as representatives, it is identified that seven MBenes (CrB, MoB, WB, Mo2B, V3B4, CrMnB2, and CrFeB2) not only have intrinsic basal plane activity for NRR with limiting potentials ranging from −0.22 to −0.82 V, but also possess superior capability of suppressing the competitive hydrogen evolution reaction. Particularly, different from the MXenes whose surface oxidation may block the active sites, once oxidized, these MBenes can catalyze NRR via the self‐activating process, reducing O*/OH* into H2O* under reaction conditions, and favoring the N2 electroreduction. As a result, the exceptional activity and selectivity, high active area (≈1019 m−2), and antioxidation nature render these MBenes as pH‐universal catalysts for NH3 production without introducing any dopants and defects.

No abstract

No abstract