A High-Throughput Screening toward Efficient Nitrogen Fixation: Transition Metal Single-Atom Catalysts Anchored on an Emerging π–π Conjugated Graphitic Carbon Nitride (g-C10N3) Substrate with Dirac Dispersion,ACS Applied Materials & Interfaces

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A High-Throughput Screening toward Efficient Nitrogen Fixation: Transition Metal Single-Atom Catalysts Anchored on an Emerging π–π Conjugated Graphitic Carbon Nitride (g-C10N3) Substrate with Dirac Dispersion
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2023-02-21 , DOI: 10.1021/acsami.2c22519
Qiang Zhang ₁ , Xian Wang ₁ , Fuchun Zhang ₂ , Chunyao Fang ₁ , Di Liu ₁ , Qingjun Zhou ₁

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TM-N_x is becoming a comforting catalytic center for sustainable and green ammonia synthesis under ambient conditions, resulting in increasing interest in single-atom catalysts (SACs) for the electrochemical nitrogen reduction reaction (NRR). However, given the poor activity and unsatisfactory selectivity of existing catalysts, it remains a long-standing challenge to design efficient catalysts for nitrogen fixation. Currently, the two-dimensional (2D) graphitic carbon-nitride substrate provides abundant and evenly distributed holes for stably supporting transition-metal atoms, which presents a fascinating prospect for overcoming this challenge and promoting single-atom NRR. An emerging holey graphitic carbon-nitride skeleton with a C₁₀N₃ stoichiometric ratio (g-C₁₀N₃) from a supercell of graphene is constructed, which provides outstanding electric conductivity for achieving high-efficiency NRR due to the Dirac band dispersion. Herein, a high-throughput first-principles calculation is carried out to evaluate the feasibility of π–d conjugated SACs resulting from a single TM atom anchored on g-C₁₀N₃ (TM = Sc–Au) for NRR. We find that W metal embedded in g-C₁₀N₃ (W@g-C₁₀N₃) can compromise the ability to adsorb the key target reaction species (N₂H and NH₂), hence acquiring an optimal NRR behavior among 27 TM-candidates. Our calculations demonstrate that W@g-C₁₀N₃ shows a well-suppressed HER ability and, impressively, a low energy cost of −0.46 V. Additionally, all-around descriptors are proposed to uncover the fundamental mechanism of NRR activity, among which a 3D volcano plot (limiting potential, screening strategy, and electron origin) uncovers the NRR activity trend, achieving a quick and high-efficiency prescreening for numerous candidates. Overall, the strategy of the structure- and activity-based TM-N_x-containing unit design will offer useful insight for further theoretical and experimental attempts.

中文翻译：

高效固氮的高通量筛选：过渡金属单原子催化剂锚定在具有狄拉克分散的新兴 π-π 共轭石墨氮化碳 (g-C10N3) 基板上

TM-N _x正在成为环境条件下可持续和绿色氨合成的令人欣慰的催化中心，导致人们对用于电化学氮还原反应 (NRR) 的单原子催化剂 (SAC) 越来越感兴趣。然而，鉴于现有催化剂的活性差和选择性不理想，设计高效的固氮催化剂仍然是一个长期存在的挑战。目前，二维 (2D) 石墨碳氮化物衬底提供了丰富且均匀分布的空穴来稳定支撑过渡金属原子，这为克服这一挑战和促进单原子 NRR 提供了迷人的前景。_{一种新兴的具有 C 10} N ₃的多孔石墨碳氮化物骨架构建了石墨烯超级电池的化学计量比 (gC ₁₀ N ₃ )，由于狄拉克能带色散，它提供了出色的导电性以实现高效 NRR。在此，进行高通量第一性原理计算以评估由锚定在 gC 10 N 3 (TM = Sc-Au) 上的单个 TM 原子产生的 π-d 共轭 SAC 用于_NRR的_可行性。我们发现嵌入 gC ₁₀ N ₃ (W@gC ₁₀ N _{3 ) 中的 W 金属会损害吸附关键目标反应物种（N}₂ H 和 NH _2）的能力)，因此在 27 个 TM 候选者中获得最佳 NRR 行为。我们的计算表明，W@gC ₁₀ N ₃显示出良好抑制的 HER 能力，令人印象深刻的是，-0.46 V 的低能量成本。此外，还提出了全方位的描述符来揭示 NRR 活动的基本机制，其中3D火山图（极限电位、筛选策略和电子起源）揭示了NRR活动趋势，实现了对众多候选人的快速高效预筛选。_{总体而言，基于结构和活性的含 TM-N x}单元设计策略将为进一步的理论和实验尝试提供有用的见解。

更新日期：2023-02-21

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