Sensitized nanocrystalline solar cells, as a promising low-cost photovoltaic device, have aroused widespread concern due to environmentfriendly properties, simple preparation, and high theoretical power conversion efficiency (PCE). [2] As an essential part of solar cells, the exceptional counter electrode (CE) should satisfy the following two conditions: good electrical conductivity and superior catalytic ability for the iodide reduction reaction (IRR). Although Pt-based CE catalysts display strong performance in accelerating the IRR process, they still cannot be widely commercialized owing to the low abundance and high cost of Pt. Considering these weaknesses, developing inexpensive, earth-abundant alternatives with high catalytic activity and good electrochemical stabilities is a crucial yet challenging mission. To date, a variety of possible replacements have been developed, such as conductive polymers, [3] metal alloy, [4] nanohybrids, [5] transition metal compounds, [6] and carbon materials. [7] Among them, carbon materials have many advantages, including but not limited to the following: i) widely sourced and cheap prices, ii) adjustable and buildable pore structure, and iii) appreciable electroconductivity and outstand electrochemical corrosion resistance. Despite these strong points, the inertness of the sp 2 or sp 3 hybrid carbon atoms in pristine carbon materials results in inferior catalytic performance in comparison with Pt-like catalysts. [8] Therefore, it is urgent to develop suitable strategies to improve the catalytic performance of carbon-based catalysts.Defect engineering, which constructs intrinsic defects and introduces external defects in carbon frameworks, is regarded as a feasible approach. It has been established that the appropriate construction of intrinsic defects in a carbon skeleton, especially hole defects (namely hierarchical pore structure), can not only regulate local electronic structure but also promote the exposure of more active sites, which is conducive to accelerating the IRR process. [9] In contrast, the introduction of external defects (mostly through metal and nitrogen doping) mainly results in the formation of new active sites on the carbon plane, so as to boost the catalytic performance of carbon-based catalysts. [10] In this respect, considering the earth-abundance and low cost, Nitrogen-coordinated metal-modified carbon is regarded as a novel frontier electrocatalyst in energy conversion devices. However, the construction of intrinsic defects in a carbon matrix remains a great challenge. Herein, N-coordinated magnetic metal (Fe, Co) modified porous carbon dodecahedrons (Fe/Co-NPCD) with a large surface area, rich intrinsic defects, and evenly distributed metal-N x species are successfully synthesized via the rational design of iron precursor and the bimetallic-organic frameworks. Because of a synergistic effect between N-coordinated dual magnetic metal active sites, the Fe/Co-NPCD exhibits exceptional electrocatalytic activity and electrochemical stability. A so...
