Photoelectrochemical(PEC)H_(2)O_(2)production through water oxidation reaction(WOR)is a promising strategy,however,designing highly efficient and selective photoanode materials remains challenging due to competitive r...Photoelectrochemical(PEC)H_(2)O_(2)production through water oxidation reaction(WOR)is a promising strategy,however,designing highly efficient and selective photoanode materials remains challenging due to competitive reaction pathways.Here,for highly enhanced PEC H_(2)O_(2)production,we present a conformal amorphous titanyl phosphate(a-TP)overlayer on nanoparticulate TiO_(2)surfaces,achieved via lysozyme-molded in-situ surface reforming.The a-TP overlayer modulates surface adsorption energies for reaction intermediates,favoring WOR for H_(2)O_(2)production over the competing O_(2)evolution reaction.Our density functional theory calculations reveal that a-TP/TiO_(2)exhibits a substantial energy uphill for the O·*formation pathway,which disfavors O_(2)evolution but promotes H_(2)O_(2)production.Additionally,the a-TP overlayer strengthens the built-in electric field,resulting in favorable kinetics.Consequently,a-TP/TiO_(2)exhibits 3.7-fold higher Faraday efficiency(FE)of 63%at 1.76 V vs.reversible hydrogen electrode(RHE)under 1 sun illumination,compared to bare TiO_(2)(17%),representing the highest FE among TiO_(2)-based WOR H_(2)O_(2)production systems.Employing the a-TP overlayer constitutes a promising strategy for controlling reaction pathways and achieving efficient solar-to-chemical energy conversion.展开更多
A versatile use of a sulfur self-doped biochar derived from Camellia japonica(camellia)flowers is demonstrated as a multifunctional catalyst for overall water splitting and a supercapacitor.The native sulfur content i...A versatile use of a sulfur self-doped biochar derived from Camellia japonica(camellia)flowers is demonstrated as a multifunctional catalyst for overall water splitting and a supercapacitor.The native sulfur content in the camellia flower facilitates in situ self-doping of sulfur,which highly activates the camellia-driven biochar(SA-Came)as a multifunctional catalyst with the enhanced electron-transfer ability and long-term durability.For water splitting,an SA-Came-based electrode is highly stable and shows reaction activities in both hydrogen and oxygen evolution reactions,with overpotentials of 154 and 362 mV at 10 mA cm^(−2),respectively.For supercapacitors,SA-Came achieves a specific capacitance of 125.42 F g^(−1)at 2 A g^(−1)and high cyclic stability in a three-electrode system in a 1 M KOH electrolyte.It demonstrated a high energy density of 34.54 Wh kg^(−1)at a power density of 1600 W kg^(−1)as a symmetric hybrid supercapacitor device with a wide working potential range of 0-1.6 V.展开更多
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government,Ministry of Science and ICT(MSIT)(NRF-2020M3D1A2102837)the Korea Institute of Energy Technology Evaluation and Planning(KETEP)grant funded by the Korea government(MOTIE)(20214000000500,training program of CCUS for the green growth)。
文摘Photoelectrochemical(PEC)H_(2)O_(2)production through water oxidation reaction(WOR)is a promising strategy,however,designing highly efficient and selective photoanode materials remains challenging due to competitive reaction pathways.Here,for highly enhanced PEC H_(2)O_(2)production,we present a conformal amorphous titanyl phosphate(a-TP)overlayer on nanoparticulate TiO_(2)surfaces,achieved via lysozyme-molded in-situ surface reforming.The a-TP overlayer modulates surface adsorption energies for reaction intermediates,favoring WOR for H_(2)O_(2)production over the competing O_(2)evolution reaction.Our density functional theory calculations reveal that a-TP/TiO_(2)exhibits a substantial energy uphill for the O·*formation pathway,which disfavors O_(2)evolution but promotes H_(2)O_(2)production.Additionally,the a-TP overlayer strengthens the built-in electric field,resulting in favorable kinetics.Consequently,a-TP/TiO_(2)exhibits 3.7-fold higher Faraday efficiency(FE)of 63%at 1.76 V vs.reversible hydrogen electrode(RHE)under 1 sun illumination,compared to bare TiO_(2)(17%),representing the highest FE among TiO_(2)-based WOR H_(2)O_(2)production systems.Employing the a-TP overlayer constitutes a promising strategy for controlling reaction pathways and achieving efficient solar-to-chemical energy conversion.
基金National Research Foundation of Korea,Grant/Award Numbers:2016M3D1A1021141,2020R1A2C2006077,2022R1A2C1012419,2021R1A4A1024129,2021R1A5A1030054Ministry of Trade,Industry and Energy(MOTIE,Korea),Grant/Award Number:20213030040590。
文摘A versatile use of a sulfur self-doped biochar derived from Camellia japonica(camellia)flowers is demonstrated as a multifunctional catalyst for overall water splitting and a supercapacitor.The native sulfur content in the camellia flower facilitates in situ self-doping of sulfur,which highly activates the camellia-driven biochar(SA-Came)as a multifunctional catalyst with the enhanced electron-transfer ability and long-term durability.For water splitting,an SA-Came-based electrode is highly stable and shows reaction activities in both hydrogen and oxygen evolution reactions,with overpotentials of 154 and 362 mV at 10 mA cm^(−2),respectively.For supercapacitors,SA-Came achieves a specific capacitance of 125.42 F g^(−1)at 2 A g^(−1)and high cyclic stability in a three-electrode system in a 1 M KOH electrolyte.It demonstrated a high energy density of 34.54 Wh kg^(−1)at a power density of 1600 W kg^(−1)as a symmetric hybrid supercapacitor device with a wide working potential range of 0-1.6 V.