Fabrication of six-atom Pd clusters regulated with different short ligands and their surface structure-dependent catalytic activities.

As model catalysts, it is necessary to study the relationship between the structure and properties of ultra-small metal nanoclusters (MNCs) and to reduce their steric hindrance as much as possible, e.g. preparing ultrasmall MNCs protected by ultra-short ligands. However, it is challenging to attain various MNCs with the same cores but different surface stabilizing ligands. Additionally, shortening the chains of protecting ligands will lead to larger MNC cores. Here, four different Pd NCs (Pd6(SC4H9)12, Pd6(SC8H17)12, Pd6(SC6(C2)H17)12 and Pd6(SC6H13)12) were successfully synthesized by a slow synthesis process. All these clusters consist of six Pd atoms and are stabilized by 12 thiols with different chain lengths and steric hindrance. The catalytic properties of the as-prepared Pd6 NCs were evaluated using the catalytic reduction of p-nitroaniline to p-phenylenediamine as a model reaction. The outcomes indicated that shortening the chain length of the protecting thiols could enhance the catalytic activity of the Pd6 NCs. Notably, stable and active ultra-small Pd6 clusters stabilized by ultra-short ligands (HSC4H9) were successfully synthesized. Although the performance of Pd6(SC4H9)12 clusters protected by the ultra-short thiols is lower than that of commercial palladium on carbon (Pd/C), they display higher stability. Interestingly, the activity of Pd6 NCs protected by ethyl-branched alkane thiols is also better than that of Pd6 NCs protected by the alkane thiol ligands with the same chain length or the same number of carbon numbers. This work provides clear evidence that the catalytic activity of atomically precise MNCs can be controlled by regulating the surface stabilizing ligands.

Homogeneous Distribution of Pt16(C4O4SH5)26 Clusters in ZIF-67 for Efficient Hydrogen Generation and Oxygen Reduction.

In recent years, based on the high catalytic activities of metal nanoclusters (MNCs) and the unique porous structure of metal-organic frameworks (MOFs), much work has focused on MOF-confined small MNCs for catalysis applications. However, the commonly used "ship-in-boat" approach is unfeasible for precisely controlling the size and composition of the formed MNCs and meanwhile often causes structural distortion/degradation. On the other hand, the "bottle-around-ship" method usually has the disadvantages that MOFs show uncontrollable self-nucleation outside the MNCs and the stabilizers on the surface of MNCs may greatly reduce their catalytic activities. In this work, monodispersed Pt16(C4O4SH5)26 clusters (Pt16(MSA)26) were first prepared and used as a precursor for the synthesis of Pt(MSA)@ZIF-67 via the typical Co-carboxylate type of linkage at the interface under ambient atmosphere. After encapsulating the Pt clusters in ZIF-67, the protecting ligands were removed under 300 °C to get surface-clean Pt16 clusters confined in ZIF-67 (Pt@ZIF-67). The obtained Pt@ZIF-67 exhibited high catalytic activity for the hydrolysis of ammonia borane that was superior to that of most of the reported noble-metal catalysts. Meanwhile, by annealing the Pt(MSA)@ZIF-67 at 800 °C to form highly conductive graphitic carbon-coated Pt NCs and Co nanoparticles (NPs) (Pt/Co@NC), the obtained composite showed high catalytic activity for the oxygen reduction reaction (ORR). The formed Pt/Co@NC showed 9.6 times higher ORR mass activity (at 0.8 V) than Pt/C. This work provides a strategy to fabricate highly dispersed and stable metal clusters confined in the porous matrix for catalysis and shows that highly porous MOFs have promising catalysis applications by combining them with other active components.

Insights into the Mo-Doping Effect on the Electrocatalytic Performance of Hierarchical CoxMoyS Nanosheet Arrays for Hydrogen Generation and Urea Oxidation.

Energy-efficient, low-cost, and highly durable catalysts for the electrochemical hydrogen evolution reaction (HER) and urea oxidation reaction (UOR) are extremely important for related sustainable energy systems. In the present work, hierarchical coassembled cobalt molybdenum sulfide nanosheets deposited on carbon cloth (CC) were synthesized as catalysts for hydrogen evolution and urea oxidation. By adjusting the doping amount of Mo, 2D nanosheets with different morphologies and compositions (CoxMoyS-CC) can be obtained. The as-prepared nanosheet materials with abundant active sites exhibit superior properties on the electrochemical HER and UOR in alkaline medium. Significantly, the Mo-doping concentration and composition of the formed nanosheets have large effects on the electrocatalytic activity. The fabricated nanosheets with optimal Mo doping (Co3Mo1S-CC) illustrate the best catalytic properties for the HER in N2-saturated 1.0 M KOH. A small overpotential (85 mV) is needed to meet the current density of 10 mA/cm2. This study indicates that the doping of an appropriate amount of molybdenum into CoS2 nanosheets can efficiently improve the catalytic performance. Also, the nanosheet catalyst exhibits an extremely high electrocatalytic activity for the UOR, and the electrochemical results indicate that a relatively low cell voltage of 1.50 V is needed to obtain the current density of 10 mA/cm2. The present work demonstrates the potential application of CoMoS nanosheets in the energy electrocatalysis area and the insights into performance-boosting through heteroatom doping and optimization of the composition and structure.

Advanced Electrocatalysts Based on Metal-Organic Frameworks.

In recent years, metal-organic frameworks (MOFs) have been wildly studied as heterogeneous catalysts due to their diversity of structures and outstanding physical and chemical properties. Meanwhile, MOFs have also been regarded as promising templates for the synthesis of conductive and electrochemically active catalysts. However, in most of the studies, high-temperature annealing is needed to transform nonconductive or low-conductive MOFs to conductive materials for electrocatalyis, during which the unique structures and intrinsic active sites in MOFs can be easily destroyed. Therefore, in recent years, different strategies have been developed for improving the catalytic performances of MOF-based composites for electrochemical reactions with no need of post-treatment. This mini-review highlights the recent advances on MOF-based structures with improved conductivities and electrochemical activities for the application in electrocatalysis. Overall, the advanced MOF-based electrocatalysts include the highly conductive and electrochemically active pristine MOFs, MOFs combined with conductive substrates, and MOFs hybridized with active materials. Finally, we propose the direction for future works on MOF-based electrocatalysts.

Fe/Ni bimetal organic framework as efficient oxygen evolution catalyst with low overpotential.

Electrochemical water-splitting is an ideal strategy to produce the promising substitutable energy source, hydrogen (H2). However, the sluggish kinetics of electrochemical oxygen evolution reaction (OER) and the prohibitive cost, low reserves and easy oxidation of noble metal-based electrocatalysts force researchers to explore efficient and low-cost electrocatalysts. Bimetal nanostructred materials are proved to have enhanced OER catalytic performances. In this study, a series of bimetallic metal-organic frameworks (Fe/Ni-MOFs) are prepared by a solvothermal method. The prepared MOFs present abundant unsaturated metal active sites for OER. The optimized Fe/Ni bimetal-MOF has low overpotentials of 236 mV at 10 mA cm-2 and 284 mV at 100 mA cm-2 for OER. In addition, in comparison with most of the previously reported OER electrocatalysts, the present MOF shows a lower Tafel slope of 49 mV dec-1. Besides, the MOF catalyst exhibits high electrochemical stability and the OER activity shows a negligible change after stability test for 15 h and 10,000 voltammetric cycles. Meanwhile, the Fe-doped Ni-MOFs show faster catalytic kinetics and higher conductivity than the monometallic Ni-MOF. This work paves a way to exploit bi- or multi-metallic MOFs with high conductivities and electrocatalytic performances for electrochemical energy conversion.