Ru–Ru₂PΦNPC and NPC@RuO₂ Synthesized via Environment‐Friendly and Solid‐Phase Phosphating Process by Saccharomycetes as N/P Sources and Carbon Template for Overall Water Splitting in Acid Electrolyte

Abstract

Although numerous ruthenium-based phosphates possess high catalytic activities for hydrogen evolution reaction (HER), most of them rely on dangerous and toxic synthesis routes. Biological slices confirm that Ru ions can penetrate the cell walls of saccharomycete, which facilitates the adsorption of Ru ions. Herein, based on a green synthesis process by saccharomycete cells as the carbon template and nitrogen/phosphorus (N/P) sources, novel Janus-like rutheniumruthenium phosphide nanoparticles embedded into a N/P dual-doped carbon matrix (Ru-Ru 2 PΦNPC) electrocatalyst for HER are synthesized. Electrochemical tests reveal that Ru-Ru 2 PΦNPC displays remarkable performance with a low overpotential of 42 mV at 10 mA cm −2 and demonstrates superior stability at a high current density in 0.5 m H 2 SO 4 . Furthermore, ruthenium oxide nanoparticles coated N/P dual-doped carbon (NPC@RuO 2 ) are also synthesized with a yolk-shell structure using saccharomycete cells as the core template and RuO 2 as a shell to isolate saccharomycete cells from the oxidation reaction during calcination in air. The NPC@RuO 2 as oxygen evolution reaction electrocatalyst possesses a low overpotential of 220 mV at 10 mA cm −2 . Finally, the Ru-Ru 2 PΦNPC is integrated as a cathode and NPC@RuO 2 is integrated as an anode to construct a two-electrode electrolyzer to enable an excellent performance for overall water splitting with a cell voltage of 1.50 V at 10 mA cm −2 in 0.5 m H 2 SO 4 .

Transition‐Metal Phosphides: Activity Origin, Energy‐Related Electrocatalysis Applications, and Synthetic Strategies

“…© 2020 Wiley-VCH GmbH yeast, PCl 3 , etc. [184][185][186][187][188][189][190][191][192] Furthermore, Table 2 lists the typical advantages and disadvantages of preparing TMPs based on phosphorus sources.…”

“…[189] Similarly, Zhou and co-workers reported saccharomycete cells as both carbon template and green biomass phosphorus source to safely synthesize the Janus-like Ru-Ru 2 P nanoparticles embedded into nitrogen, phosphorus dual-doped carbon as an efficient electrocatalyst for HER. [188] Pyrolysis of phosphorusbased porous polymer precursors and metal-containing anions precursor is another way to obtain TMPs. [235] In addition, the ionic liquid was reported as the phosphorus precursor to prepare TMPs.…”

Charge Redistribution Caused by S,P Synergistically Active Ru Endows an Ultrahigh Hydrogen Evolution Activity of S‐Doped RuP Embedded in N,P,S‐Doped Carbon

“…Undoubtedly, the S-RuP@NPSC-900 possessed overwhelming advantage in current density after normalized by Ru loading, which revealed the high utilization of Ru. Comparing with current relevant literature with the overpotential of 50 mV, the HER mass specific activity of S-RuP@NPSC-900 (871.50 A g −1 ) with an ultralow loading of Ru (0.8 wt%) was larger than those of the recently reported Ru-based HER electrocatalysts, such as RuP 2 @NPC (64.38 A g −1 ), [47] Ru-Ru 2 PΦNPC (2.96 A g −1 ), [40] RuP/CC (38.40 A g −1 ), RuP 2 /CC(7.69 A g −1 ), [41] and the ultrasmall Ru 2 P NPs@GO (765.63 A g −1 ), [48] which showed that S-RuP@NPSC-900 was a promising and competitive HER catalyst.…”

“…In addition, PZS used as solid phosphorus source replaced the gas phosphating reaction using the hypophosphites [31] and hydrothermal reaction using red phosphorus or trioctylphosphine (TOP) [38,39] to avoid producing toxic, flammable polluting tail gas. [40] The obtained S-RuP@NPSC as HER electrocatalyst possessed the high catalytic activity with an overpotential of 92 mV to reach a current density of 10 mA cm −2 and rough catalytic stability in alkaline solution. It is worth noting that the S-RuP@NPSC possessed high utilization of Ru precious metals, the according mass specific activity was 22.88 times than that of 20% Pt/C with the overpotential of 250 mV.…”

Selective Loading of Atomic Platinum on a RuCeOx Support Enables Stable Hydrogen Evolution at High Current Densities

“…As shown in Figure S13c and S14d, Cl-Pt-O-Ru and Pt-O-Ce seem to be the favorable active site for HER since its DG H* value (0.095 and 0.034 eV, respectively) are closer to zero than the corresponding values for Pt-O-Ru (site-A, À0.15 eV). [17] However, when a catalyst contains more than one kind of active site, the hydrogen spillover effect between different sites, namely the H* transfer from a hydrogen-enriched phase (more negative DG H* ) to a hydrogen-deficient phase (more positive DG H* ), can greatly affect the overall catalytic activity. Therefore, we also calculated the DG H* values for the possible adjacent sites: the calculated values for the O atom in Pt-O-Ru (site-B), RuO 2 (110) plane (site-C), Ce-O-Pt, and CeO 2 (111) plane were À0.014, 0.23, 0.04, and À0.34 eV, respectively (Figure S13 and S14).…”