Electron Delocalization Disentangles Activity-Selectivity Trade-Off of Transition Metal Phosphide Catalysts in Oxidative Desulfurization.

Breaking the activity-selectivity trade-off has been a long-standing challenge in catalysis. Here, we proposed a nanoheterostructure engineering strategy to overcome the trade-off in metal phosphide catalysts for the oxidative desulfurization (ODS) of fuels. Experimental and theoretical results demonstrated that electron delocalization was the key driver to simultaneously achieve high activity and high selectivity for the molybdenum phosphide (MoP)/tungsten phosphide (WP) nanoheterostructure catalyst. The electron delocalization not only promoted the catalytic pathway transition from predominant radicals to singlet oxygens in H2O2 activation but also simultaneously optimized the adsorption of reactants and intermediates on Mo and W sites. The presence of such dual-enhanced active sites ideally compensated for the loss of activity due to the nonradical catalytic pathway, consequently disentangling the activity-selectivity trade-off. The resulting catalyst (MoWP2/C) unprecedentedly achieved 100% removal of thiophenic compounds from real diesel at an initial concentration of 2676 ppm of sulfur with a high turnover frequency (TOF) of 105.4 h-1 and a minimal O/S ratio of 4. This work provides fundamental insight into the structure-activity-selectivity relationships of heterogeneous catalysts and may inspire the development of high-performance catalysts for ODS and other catalytic fields.

Efficient Proton Transfer and Charge Separation within Covalent Organic Frameworks via Hydrogen-Bonding Network to Boost H2O2 Photosynthesis.

Photocatalytic synthesis based on the oxygen reduction reaction (ORR) has shown great promise for H2O2 production. However, the low activity and selectivity of 2e- ORR result in a fairly low efficiency of H2O2 production. Herein, we propose a strategy to enhance the proton-coupled electron transfer (PCET) process in covalent organic frameworks (COFs), thereby significantly boosting H2O2 photosynthesis. We demonstrated that the construction of a hydrogen-bonding network, achieved by anchoring the H3PO4 molecular network on COF nanochannels, can greatly improve both proton conductivity and photogenerated charge separation efficiency of COFs. Thus, COF@H3PO4 exhibited superior photocatalytic performance in generating H2O2 without sacrificial agents, with a solar-to-chemical conversion efficiency as high as 0.69%. Results indicated that a much more localized spatial distribution of energy band charge density on COF@H3PO4 led to efficient charge separation, and the small energy barrier of the rate-limiting step from *OOH to H2O2 endowed COF@H3PO4 with higher 2e- ORR selectivity.

Electronic Phosphide-Support Interactions in Carbon-Supported Molybdenum Phosphide Catalysts Derived from Metal-Organic Frameworks.

Interfacial interaction in carbon-supported catalysts can offer geometric, electronic, and compositional effects that can be utilized to regulate catalytically active sites, while this is far from being systematically investigated in carbon-supported phosphide catalysts. Here, we proposed a novel concept of electronic phosphide-support interaction (EPSI), which was confirmed by using molybdenum phosphide (MoP) supported on nitrogen-phosphorus codoped carbon (NPC) as a model catalyst (MoP@NPC). Such a strong EPSI could not only stabilize MoP in a low-oxidation state under environmental conditions but also regulate its electronic structure, leading to reduced dissociation energy of the oxygen-containing intermediates and enhancing the catalytic activity for oxidative desulfurization. The removal of dibenzothiophene over the MoP@NPC was as high as 100% with a turnover frequency (TOF) value of 0.0027 s-1, which was 33 times higher than that of MoP without EPSI. This work will open new avenues for the development of high-performance supported phosphide catalysts.