Exploring efficient and cost-effective catalysts to replace precious metal catalysts, such as Pt, for electrocatalytic oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) holds great promise for renewable energy technologies. Herein, we prepare a type of Co catalyst with single-atomic Co sites embedded in hierarchically ordered porous N-doped carbon (Co-SAS/HOPNC) through a facile dual-template cooperative pyrolysis approach. The desirable combination of highly dispersed isolated atomic Co-N4 active sites, large surface area, high porosity, and good conductivity gives rise to an excellent catalytic performance. The catalyst exhibits outstanding performance for ORR in alkaline medium with a half-wave potential (E1/2) of 0.892 V, which is 53 mV more positive than that of Pt/C, as well as a high tolerance of methanol and great stability. The catalyst also shows a remarkable catalytic performance for HER with distinctly high turnover frequencies of 0.41 and 3.8 s−1 at an overpotential of 100 and 200 mV, respectively, together with a long-term durability in acidic condition. Experiments and density functional theory (DFT) calculations reveal that the atomically isolated single Co sites and the structural advantages of the unique 3D hierarchical porous architecture synergistically contribute to the high catalytic activity.

A novel polymer encapsulation strategy to synthesize metal isolated-single-atomic-site (ISAS) catalysts supported by porous nitrogen-doped carbon nanospheres is reported. First, metal precursors are encapsulated in situ by polymers through polymerization; then, metal ISASs are created within the polymer-derived p-CN nanospheres by controlled pyrolysis at high temperature (200-900 °C). Transmission electron microscopy and N sorption results reveal this material to exhibit a nanospheric morphology, a high surface area (≈380 m g ), and a porous structure (with micropores and mesopores). Characterization by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure confirms the metal to be present as metal ISASs. This methodology is applicable to both noble and nonprecious metals (M-ISAS/p-CN, M = Co, Ni, Cu, Mn, Pd, etc.). In particular, the Co-ISAS/p-CN nanospheres obtained using this method show comparable (E = 0.838 V) electrochemical oxygen reduction activity to commercial Pt/C with 20 wt% Pt loading (E = 0.834 V) in alkaline media, superior methanol tolerance, and outstanding stability, even after 5000 cycles.

Herein, we report efficient single copper atom catalysts that consist of dense atomic Cu sites dispersed on a three-dimensional carbon matrix with highly enhanced mesoporous structures and improved active site accessibility (Cu-SA/NC­(meso)). The ratio of +1 to +2 oxidation state of the Cu sites in the Cu-SA/NC­(meso) catalysts can be controlled by varying the urea content in the adsorption precursor, and the activity for ORR increases with the addition of Cu1+ sites. The optimal Cu1+-SA/NC­(meso)-7 catalyst with highly accessible Cu1+ sites exhibits superior ORR activity in alkaline media with a half-wave potential (E 1/2) of 0.898 V vs RHE, significantly exceeding the commercial Pt/C, along with high durability and enhanced methanol tolerance. Control experiments and theoretical calculations demonstrate that the superior ORR catalytic performance of Cu1+-SA/NC­(meso)-7 catalyst is attributed to the atomically dispersed Cu1+ sites in catalyzing the reaction and the advantage of the introduced mesoporous structure in enhancing the mass transport.

Noble metals play a momentous role in heterogeneous catalysis but still face a huge challenge in selectivity control. Herein, we report isolating contiguous Pt atoms and forming Pt-Zn intermetallic nanoparticles as an effective strategy to optimize the selectivity of Pt catalysts. Contiguous Pt atoms are isolated into single atoms and Pt-Zn intermetallic nanoparticles are formed which are supported on hollow nitrogen-doped carbon nanotubes (PtZn/HNCNT), as confirmed by aberration-corrected high-resolution transmission electron microscopy and X-ray absorption spectrometry measurements. Interestingly, this PtZn/HNCNT catalyst promotes the hydrogenation of 4-nitrophenylacetylene to 4-aminophenylacetylene with a much higher conversion ( > 99%) and selectivity (99%) than the comparison samples with Pt isolated-single-atomic-sites (Pt/HNCNT) and Pt nanoparticles (Pt/CN). Further density functional theory (DFT) calculations disclose that the positive Zn atoms assist the adsorption of nitro group and Pt-Zn intermetallic nanoparticles facilitate the hydrogenation on nitro group kinetically.

Clinical inhibitors Darunavir (DRV) and Amprenavir (APV) are less effective on HIV-2 protease (PR2) than on HIV-1 protease (PR1). To identify molecular basis associated with the lower inhibition, molecular dynamics (MD) simulations and molecular mechanics Poisson-Boltzmann surface area (MM-PBSA) calculations were performed to investigate the effectiveness of the PR1 inhibitors DRV and APV against PR1/PR2. The rank of predicted binding free energies agrees with the experimental determined one. Moreover, our results show that two inhibitors bind less strongly to PR2 than to PR1, again in agreement with the experimental findings. The decrease in binding free energies for PR2 relative to PR1 is found to arise from the reduction of the van der Waals interactions induced by the structural adjustment of the triple mutant V32I, I47V and V82I. This result is further supported by the difference between the van der Waals interactions of inhibitors with each residue in PR2 and in PR1. The results from the principle component analysis suggest that inhibitor binding tends to make the flaps of PR2 close and the one of PR1 open. We expect that this study can theoretically provide significant guidance and dynamics information for the design of potent dual inhibitors targeting PR1/PR2.