CHEMICAL ENGINEERING JOURNAL
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2026
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IF 12.5
Mingfu Li,Pingjun Zhang,Jiannan Qin,Hao Cheng,Qian Yu,Liqun Jiang
Photocatalysis has demonstrated great potential in the conversion of biomass, but the design of single-atom photocatalysts for the selective upgrading of glucose is rarely achieved. Here, we report a manganese doped g-C 3 N 4 (Mn SA -CN) single-atom photocatalyst by the impregnation-pyrolysis method, which achieves 34.6% glucaric acid (GAA) yield and 72.6% glucose conversion. Physicochemical characterizations indicate that the atomically dispersed Mn N 4 sites serve as the key catalytic centers, which not only optimize the electronic structure by narrowing the band gap, but also significantly promote the separation of photo-generated charge carriers. Additionally, the free radical scavenging experiments indicated that the hydroxyl radical is the main species for promoting the photocatalytic conversion of glucose. Furthermore, the GAA yield maintained over 33.0% after the catalyst was recycled five times. DFT calculation reveals that the Mn N 4 coordination structure increases the glucose adsorption and electron transfer, thereby reducing the overall reaction energy barrier and promoting the photocatalytic synthesis of GAA. This work offers fundamental insights at the atomic level for the rational design of single-atom photocatalysts toward sustainable biomass conversion.
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CHINESE JOURNAL OF CATALYSIS
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2024
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IF 15.7
Yuan Jiang,Ji Yang,Mu-Lin Li,Xue-Jia Wang,Na Yang,Wei-Ping Chen,Jin-Chao Dong,Jian-Feng Li
ABSTRACT Metal-nitrogen-carbon single-atom catalysts (M-N-C SACs) have emerged as a highly promising material for ammonia synthesis from electrocatalytic nitrate reduction due to their isolated metal site and capacity to prevent the N–N coupling. However, understanding the structure-activity relationship at molecular level remains challenging because of the inhomogeneous M N x structure presented in current synthesized M-N-C catalysts. In this study, we utilized metal phthalocyanine ( M Pc) as a model platform catalyst containing a uniform and well-defined M N 4 center to unravel their intrinsic activity tendency toward ammonia synthesis from nitrate reduction, both experimentally and theoretically. Our experimental results exhibit a significant activity difference for ammonia production in the order of FeN 4 > CuN 4 > NiN 4 > MnN 4 > CoN 4 > ZnN 4 , and among which the FeN 4 site delivers much higher faradic efficiency and the highest turnover frequency of 83.3% and 4395.2 h –1 at –1.0 V vs . RHE, respectively. Density-functional theory calculations indicates that, compared to CoN 4 and MnN 4 , the FeN 4 site not only has appropriate adsorption strength for NO x intermediate species, but also has certain inhibitory effects on hydrogen evolution reaction process. These findings provide systematic and reliable guidance for catalyst synthesis toward nitrate reduction to NH 3 from both the experimental and computational perspectives.
研究领域:
催化
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电化学
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材料科学
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理论化学
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Journal of Energy Storage
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2026
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IF 9.8
Yaqian Dong,Shuyu Yue,Tiehua Ma,Yaohui Zhang
The development of efficient and stable oxygen reduction reaction (ORR) catalysts is critical for advancing sustainable energy technologies, particularly rechargeable zinc-air batteries (ZABs) which offer high theoretical energy density, inherent safety, and cost-effectiveness compared to other metal-air systems. However, the widespread application of ZABs is hindered by the sluggish kinetics of the air cathode ORR, and state-of-the-art Pt-based catalysts suffer from high cost, susceptibility to poisoning, and inadequate durability in neutral media. To address this challenge, non-precious metal catalysts represented by metal‑nitrogen‑carbon dopants have attracted significant attention due to their geometrically constrained coordination environments that resist hydrolytic dissociation and electronic structures capable of circumventing specific adsorption poisoning pathways. Herein, we report a molecularly engineered manganese single-atom catalyst (MnNC-0.5) synthesized via a cyano-amino coordination strategy coupled with MgO-templated pyrolysis. This approach creates well-defined Mn N 4 sites adjacent to -CN functional groups within a hierarchical porous carbon matrix. The catalyst exhibits exceptional ORR activity across the entire pH spectrum, with half-wave potentials of 0.89 V in 0.1 M KOH, 0.77 V in 0.5 M H 2 SO 4 , and 0.69 V in 0.1 M PBS. It also demonstrates remarkable stability, retaining over 90% of its initial current after 35,000 s of continuous operation. Density functional theory (DFT) calculations reveal that the adjacent -CN group electronically modulates the Mn N 4 center, optimizing the adsorption free energy of oxygen intermediates and thereby enhancing the intrinsic activity. When employed as an air cathode in a liquid ZAB, the MnNC-0.5-based device achieves a peak power density of 193.4 mW cm −2 and a high specific energy density of 1094 Wh kg Zn −1 , outperforming the Pt/C benchmark. This work provides a viable molecular-engineering strategy for designing high-performance, pH-universal ORR electrocatalysts for next-generation energy conversion and storage devices.
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APPLIED CATALYSIS B-ENVIRONMENTAL
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2026
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IF 21.1
Yaxiong Zeng,Jie Yu,Beimeng Qi,Fang Tao,Xiaotian Yang,Yulin Wang,Xiaoguang Duan,Hailu Fu
Regulating the microenvironment of single-atom catalysts (SACs) is critical for steering ozone (O 3 ) activation toward selective on-demand reactive species generation. While first-shell coordination engineering modulates the center metal activity, it often disrupts the robust Mn-N 4 symmetry and thus compromises structural stability. Here, we developed atomically dispersed Mn-N 4 -S sites (S-MnN 4 ) that feature sulfur doping in the second coordination shell for catalytic ozonation and water pollutant degradation. Second-shell sulfur incorporation subtly elevated the d -band center and increased the spin state of Mn from low to intermediate, enhancing O 3 adsorption, dissociation and the preferred generation of high-valent Mn(IV)=O species. Consequently, S-MnN 4 achieved a 2.7-fold higher ozone utilization efficiency and double the turnover frequency versus pristine MnN 4 which catalyzed O 3 to primarily yield singlet oxygen. A continuous-flow system using a S-MnN 4 -packed column reactor demonstrated efficient chemical oxygen demand removal and exceptional durability over 170 h for the treatment of real-world wastewater. This work highlights second-shell coordination engineering as a feasible approach to overcome SAC activity-stability trade-off, advancing rational SAC design toward a sustainable environmental remediation.
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