$sztubm Efgfdu Fohjoffsjoh PG #J 5F Oboptiffut CZ $F Epqjoh Gps Fggjdjfoufmfduspdbubmzujdojusphfosfevdujpo

Research Article
‫ڀ‬
ISSN 1998-0124 CN 11-5974/O4

2023, 16(5): 6544−6551 https://doi.org/10.1007/s12274-022-5319-x
‫ڀ‬
$SZTUBM EFGFDU FOHJOFFSJOH PG #J5F OBOPTIFFUT CZ $F EPQJOH GPS
FGGJDJFOUFMFDUSPDBUBMZUJDOJUSPHFOSFEVDUJPO
Jianli Nan1,2, Yongqin Liu1,2, Daiyong Chao1,2, Youxing Fang2, and Shaojun Dong1,2,3 ( Ⴃ)
‫ܮ‬
$PMMFHFPG$IFNJTUSZ +JMJO6OJWFSTJUZ $IBOHDIVO $IJOB
‫ܮ‬
$IBOHDIVO4UBUF,FZ-BCPSBUPSZPG&MFDUSPBOBMZUJDBM$IFNJTUSZ $IBOHDIVO*OTUJUVUFPG"QQMJFE$IFNJTUSZ $IJOFTF"DBEFNZPG4DJFODFT
$IBOHDIVO $IJOB
‫ܮ‬
6OJWFSTJUZPG4DJFODFBOE5FDIOPMPHZPG$IJOB )FGFJ $IJOB
‫ڀ‬
ª‫ڀ‬5TJOHIVB6OJWFSTJUZ1SFTT
3FDFJWFE4FQUFNCFS3FWJTFE/PWFNCFS"DDFQUFE/PWFNCFS
"#453"$5
Electrochemical nitrogen reduction reaction (NRR) is a promising method for the synthesis of ammonia (NH3). However, the
electrochemical NRR process remains a great challenge in achieving a high NH3 yield rate and a high Faradaic efficiency (FE)
due to the extremely strong N≡N bonds and the competing hydrogen evolution reaction (HER). Recently, bismuth telluride
(Bi2Te3) with two-dimensional layered structure has been reported as a promising catalyst for N2 fixation. Herein, to further
enhance its NRR activity, a general doping strategy is developed to introduce and modulate the crystal defects of Bi2Te3
nanosheets by adjusting the amount of Ce dopant (denoted as Cex-Bi2Te3, where x represents the designed molar ratio of Ce/Bi).
Meanwhile, the crystal defects can be designed and controlled by means of ion substitution and charge compensation. At
−0.60 V versus the reversible hydrogen electrode (RHE), Ce0.3-Bi2Te3 exhibits a high NH3 yield (78.2 μg·h−1·mgcat−1), a high FE
(19.3%), and excellent structural and electrochemical stability. Its outstanding catalytic activity is attributed to the tunable crystal
defects by Ce doping. This work not only contributes to enhancing the NRR activity of Bi2Te3 nanosheets, but also provides a
reliable approach to prepare high-performance electrocatalysts by controlling the type and concentration of crystal defects for
artificial N2 fixation.
,&:803%4
electrochemical ammonia synthesis, nitrogen reduction reaction, (bismuth telluride) Bi2Te3 nanosheets, Ce doping, crystal
defects
‫ڀ‬
‫*ڀڀڀڀ‬OUSPEVDUJPO
‫ڀ‬
IBWFUXPGFBUVSFT5IFZDBOBDDFQUMPOFQBJSFMFDUSPOTGPSFGGJDJFOU
BETPSQUJPO PG / BOE DBO EPOBUF FMFDUSPOT UP UIF BOUJCPOEJOH
5IFQSPEVDUJPOPGBNNPOJB /) GSPN/BOE)CZUIFXFMM PSCJUBMT PG EJOJUSPHFO NPMFDVMFT UP BDUJWBUF UIF /≡/ USJQMFCPOE
LOPXO)BCFSo#PTDIQSPDFTTIBTCFFOTVDDFTTGVMGPSNPSFUIBOB
<o>
DFOUVSZ QSPWJEJOHPGUIFOJUSPHFOTPVSDFGPSGFSUJMJ[FSTBOE
'PS UIF EFWFMPQNFOU PG IJHIMZ FGGFDUJWF FMFDUSPDIFNJDBM /33
BO BMUFSOBUJWF FOFSHZ DBSSJFS XJUI IJHI FOFSHZ EFOTJUZ < >
DBUBMZTUT DSZTUBM EFGFDU FOHJOFFSJOH NBUFSJBMT BSF QSPNJTJOH
"MUIPVHI / JT OBUVSBMMZ BCVOEBOU UIF IJHI CPOE FOFSHZ PG UIF
DBOEJEBUFT GPS QSBDUJDBM BQQMJDBUJPOT < > $SZTUBM EFGFDUT DBO
/≡/USJQMFCPOE L+rNPM¦ NBLFT/BSFMVDUBOUSFBDUBOUUIBU
JOEVDF TUSVDUVSBM NPEVMBUJPO PG BUPNT BOE FMFDUSPOT QSPWJEJOH
SFRVJSFTTJHOJGJDBOUMZIJHIFOFSHZDPTU< >*OBEEJUJPO UIFVTFPG
GPTTJMGVFMTBMTPMFBETUPBTJHOJGJDBOUMFWFMPG$0FNJTTJPO< > VOJRVF BDUJWF TJUFT GPS OJUSPHFO BETPSQUJPO BOE BDUJWBUJPO 6Q UP
&MFDUSPDIFNJDBM/GJYBUJPO BMTPLOPXOBT/SFEVDUJPOSFBDUJPO OPX /33 DBUBMZTUT XJUI WBDBODZ EFGFDUT DBUDI NPTU BUUFOUJPOT
/33 DBO CF QSPDFTTFE VOEFS BNCJFOU DPOEJUJPOT BOE VTF BO 'PS FYBNQMF PYZHFO WBDBODJFT PO USBOTJUJPO NFUBM PYJEFT BSF
JOFYQFOTJWFBRVFPVTFMFDUSPMZUFBTUIFQSPUPOTPVSDF BOEUIVTJT GPVOE UP DPOUSJCVUF UP /33 CZ FOIBODJOH UIF BETPSQUJPO PG
DPOTJEFSFEBTBQSPNJTJOHBMUFSOBUJWFNFUIPE<o>)PXFWFS UIF EJOJUSPHFO NPMFDVMFT < o> /PUBCMZ UXPEJNFOTJPOBM
EJSFDU USBOTGFS PG FMFDUSPOT GSPN UIF FMFDUSPEF TVSGBDF UP /≡/ NBUFSJBMT XJUI VMUSBUIJO UIJDLOFTT BOE MBSHF TVSGBDF BSFB VTVBMMZ
SFRVJSFT PWFSDPNJOH B SBUIFS IJHI FOFSHZ CBSSJFS TP UIF DBO BGGPSE NPSF PQFO BDUJWF TJUFT XIJDI BMMPX EFDSFBTF JO UIF
EFWFMPQNFOU PG BDUJWF DBUBMZUJD DFOUFST JT DSVDJBM UP BDIJFWF BCTPSCFEFOFSHZPGUIFSFBDUBOUTPOUIFDBUBMZTUT<>*OBEEJUJPO
FGGFDUJWF/GJYBUJPO XIJDIDBOHSFBUMZSFEVDFUIFMBSHFBDUJWBUJPO UIFJOUSPEVDUJPOPGIFUFSPBUPNJDEPQBOUTDBOGVSUIFSDIBOHFUIF
FOFSHZCBSSJFSPG/≡/BOEQSPNPUFJUTEJTTPDJBUJPO<>%VFUP DIBSHF EJTUSJCVUJPO BOE UIVT QSPNPUF UIF QSPEVDUJPO PG OFX
UIF FYJTUFODF PG XBUFS NPMFDVMFT BU BO PWFSXIFMNJOH MFWFM EFGFDUT BOE DBUBMZUJD BDUJWFTJUFT <o> 5IFSFGPSF UIF
DPNQBSFE UP UIF MJNJUFE TPMWBUFE / UIF FOSJDINFOU PG DPOTUSVDUJPO PG BCVOEBOU DSZTUBM EFGFDUT PO UXPEJNFOTJPOBM
FMFDUSPDBUBMZUJD DFOUFST UP QFSGPSN UIF /33 SBUIFS UIBO UIF NBUFSJBMT WJB JPO EPQJOH DBO CF SBUJPOBM UP UIF EFTJHO PG IJHI
IZESPHFO FWPMVUJPO SFBDUJPO )&3 JT EFNBOEFE UP BDIJFWF UIF QFSGPSNBODF/33DBUBMZTUT
HPBM <o> 5IF BDUJWF DFOUFST PG FMFDUSPDIFNJDBM /33 NVTU "T B UZQJDBM UXPEJNFOTJPOBM MBZFSFE OBOPNBUFSJBM CJTNVUI
‫ڀ‬
"EESFTTDPSSFTQPOEFODFUPEPOHTK!DJBDBDDO
Nano Res. 2023, 16(5): 6544–6551 6545
‫ڀ‬
UFMMVSJEF #J5FIBTCFFOXJEFMZVTFEJOFMFDUSPDBUBMZTJTEVFUPJUT EFUBJMT DBO CF GPVOE JO UIF &MFDUSPOJD 4VQQMFNFOUBSZ .BUFSJBM
TQFDJBMNFUBMMJDTVSGBDFTUBUFBOEMBSHFMBZFSTQBDJOH<o>5IF &4.
XJEFTQSFBEVTFPG#J5FJODBUBMZTJTBMXBZTCFOFGJUTGSPNUIFSJDI
EFGFDUT 'PS FYBNQMF )VBOHT HSPVQ QSFQBSFE VMUSBUIJO #J5F ‫ڀڀڀڀ‬3FTVMUTBOEEJTDVTTJPO
‫ڀ‬
OBOPTIFFUT DPOUBJOJOH B MBSHF OVNCFS PG UFMMVSJVN WBDBODJFT CZ

FMFDUSPDIFNJDBMSFEVDUJPO BOEEFNPOTUSBUFEUIFJSFYDFMMFOU/33
3.1 Material characterization
JOUSJOTJDBDUJWJUZ<>*UJTXFMMLOPXOUIBUIFUFSPBUPNEPQJOHJTB
DPNNPO TUSBUFHZ UP HFOFSBUF DSZTUBM EFGFDUT < > 8BOHT 5IF GMPX EJBHSBN GPS UIF TPMWPUIFSNBM QSFQBSBUJPO PG $FEPQFE
HSPVQVTFEJSPOJPOJSSBEJBUJPOUPHFOFSBUFWBSJPVTDSZTUBMEFGFDUT #J5F OBOPTIFFUT JT TIPXO JO 'JH4 JO UIF &4. #PUI QVSF
PO UIF TVSGBDF PG #J5F OBOPTIFFUT UP JNQSPWF UIF )&3 #J5F 'JH B BOE $F#J5F 'JH C FYIJCJU IFYBHPOBM
QFSGPSNBODF PG UIF NBUFSJBMT <> *O BEEJUJPO QSFWJPVT SFQPSUT OBOPTIFFU NPSQIPMPHZ BT TIPXO JO UIF TDBOOJOH FMFDUSPO
IBWFDPOGJSNFEUIBU$FCBTFENBUFSJBMTBSFBDUJWFFMFDUSPDBUBMZTUT NJDSPTDPQZ 4&. JNBHFT JOEJDBUJOH UIBU $F EPQJOH IBT
GPS /33 <o> 5IFSFGPSF UIF FYQMPSBUJPO CZ JOUSPEVDJOH $F JOTJHOJGJDBOUFGGFDUPOUIFQBSUJDMFTJ[FBOETIBQF5IFUSBOTNJTTJPO
JOUP #J5F OBOPTIFFUT UISPVHI EPQJOH UP JOEVDF UIF DSZTUBM FMFDUSPO NJDSPTDPQZ 5&. JNBHFT PG #J5F OBOPTIFFUT
EFGFDUTJTFYQFDUFEUPBDIJFWFUIFFGGFDUJWF/33 'JH D BOE$F#J5F 'JH E GVSUIFSSFWFBMUIFIFYBHPOBM
)FSFJO XFSFQPSUFE$FEPQFE#J5FOBOPTIFFUTXJUIUVOBCMF NPSQIPMPHZPGUIFTBNQMFTXJUIBQBSUJDMFTJ[FPGBCPVUON
DSZTUBMEFGFDUTTZOUIFTJ[FECZUIFTPMWPUIFSNBMNFUIPEBTFGGJDJFOU BOE TIPX UIBU $F EPQJOH EPFT OPU IBWF B OPUBCMF FGGFDU PO UIF
FMFDUSPDBUBMZTUT GPS /33 #J5F JT B DPNQPVOE XJUI UIF MBZFSFE QBSUJDMFTJ[F XIJDIJTDPOTJTUFOUXJUIUIF4&.SFTVMUT*OBEEJUJPO
TUSVDUVSF BOE DSZTUBM EFGFDUT DBO CF HFOFSBUFE JO UIF IPTU CZ BUPNJD GPSDF NJDSPTDPQZ "'. JNBHFT TIPX UIBU #J5F
EPQJOH XJUI IFUFSPBUPNT $PNQBSFE UP QSJTUJOF #J5F $F OBOPTIFFUTIBWFBGMBUTVSGBDFBOEUIFJSUIJDLOFTTJTBSPVOEON
#J5FFYIJCJUFEBIJHI/)ZJFMEPGϪHrI¦rNHDBU¦BOEBIJHI 'JH F XIJMF $F#J5F OBOPTIFFUT BSF TJHOJGJDBOUMZ UIJOOFS
'BSBEBJD FGGJDJFODZ '& PG BU ¦ 7 JO . /B40 BOE UIF TVSGBDF CFDPNFT SPVHIFS 'JH G 5IFO UIF
TPMVUJPO "T BO FGGJDJFOU /33 FMFDUSPDBUBMZTU UIF JNQSPWFE ZJFME DPNQPTJUJPOPG$FY#J5FXBTGVSUIFSEFUFSNJOFEWJBUIFFOFSHZ
BOE'&DBOCFBUUSJCVUFEUPUIFGPMMPXJOHSFBTPOT 5IFEFGFDUT EJTQFSTJWF 9SBZ TQFDUSPTDPQZ &%4 BOE JOEVDUJWFMZ DPVQMFE
FYJTUJOH JO $F#J5F DBO TFSWF BT BDUJWF TJUFT UP QSPNPUF / QMBTNB PQUJDBM FNJTTJPO TQFDUSPNFUFS *$10&4 "T TIPXO JO
BETPSQUJPO BOE BDUJWBUJPO UIF TQFDJGJD TVSGBDF BSFB JT 5BCMFT4BOE4JOUIF&4. UIFDPOUFOUPG#JEFDSFBTFTHSBEVBMMZ
NBYJNJ[FE GPS UIF UXPEJNFOTJPOBM TUSVDUVSF XIJDI QSPWJEFT B
XJUIJODSFBTJOH$F XIJDINFBOTUIBU#JJTSFQMBDFECZ$FJOUIF
QPUFOUJBMMZ IJHI EFOTJUZ PG BDUJWF TJUFT BOE BMTP JODSFBTFT UIF
$FY#J5FTBNQMFT*OBEEJUJPO UIFWBMVFPG5F $F #J EFDSFBTFT
TVSGBDFBDDFTTJCJMJUZUPSFBDUBOUTBOE‫ ڀ‬UIFJOQMBOFDPOEVDUJWJUZ
XJUI NPSF $F EPQJOH JNQMZJOH BO JODSFBTF JO 5F WBDBODJFT
PG UIF NBUFSJBM JODSFBTFT BGUFS EPQJOH *U QSPWJEFT CFOFGJUT JO
FMFDUSPDIFNJDBMSFBDUJPOT XIFSFUIFIJHIFSDPOEVDUJWJUZHFOFSBMMZ 'JHVSFT H o K TIPXUIFIJHIBOHMFBOOVMBSEBSLGJFMETDBOOJOH
FOTVSFT NPSF FGGJDJFOU VTF PG UIF FMFDUSJDBM FOFSHZ .PSFPWFS UIF 5&. )""%'45&. JNBHFPG$F#J5FBOEJUT&%4FMFNFOU
DBUBMZTU BMTP EFNPOTUSBUFE UIF FYDFMMFOU TUSVDUVSBM TUBCJMJUZ BOE NBQQJOH JNBHFT XIJDI EFNPOTUSBUF UIBU $F #J BOE 5F BSF
FMFDUSPDIFNJDBMEVSBCJMJUZ VOJGPSNMZEJTUSJCVUFE
'JHVSF B TIPXT UIF 9SBZ EJGGSBDUJPO 93% QBUUFSOT PG UIF
QVSF #J5F OBOPTIFFUT BOE $FY#J5F 'PS UIFTF TBNQMFT UIF
‫&ڀڀڀڀ‬YQFSJNFOUBM
‫ڀ‬
TJNJMBS QFBLT DBO CF PCTFSWFE BU ¡ ¡ BOE ¡
DPSSFTQPOEJOH UP UIF BOE QMBOFT PG
2.1 Synthesis of Cex-Bi2Te3 SIPNCPIFESBM #J5F 1%' SFTQFDUJWFMZ <> *O
$FY#J5F OBOPTIFFUT XFSF TZOUIFTJ[FE CZ B GBDJMF POFTUFQ BEEJUJPO OPTJHOBMTBTTPDJBUFEXJUINFUBMMJD$FBOEDFSJVNPYJEFT
TPMWPUIFSNBMNFUIPE5ZQJDBMMZ NH#J /0 r)0 NH BSF EFUFDUFE JO UIF 93% QBUUFSOT PG UIF $FY#J5F *O UIF
/B5F0 NH /B0) NH QPMZWJOZMQZSSPMJEPOF 171 NBHOJGJFE93%QBUUFSOT 'JH4JOUIF&4. JUJTGPVOEUIBUUIF
BOEBDFSUBJOBNPVOUPG$F /0 r)0 BOENH UISFF QFBLT PG $FY#J5F BSF CSPBEFOFE BOE QPTJUJWF TIJGUFE
XFSFEJTTPMWFEJON-PGFUIZMFOFHMZDPM &( 5IFNJYUVSFXBT TMJHIUMZ DPNQBSFE UP UIPTF PG UIF PSJHJOBM #J5F 5IF CSPBEFOFE
TUJSSFE UP DMFBS TPMVUJPO UIFO USBOTGFSSFE UP B N- 5FGMPO QFBLTJNQMZUIBUUIFJOUSPEVDUJPOPG$FEFDSFBTFTUIFDSZTUBMMJOJUZ
TUBJOMFTTTUFFMBVUPDMBWFBOEIFBUFEBU¡$GPSI5IFCMBDL PGUIFPSJHJOBMTUSVDUVSF<>8JUIJODSFBTJOH$F DPODFOUSBUJPO
QSPEVDU XBT DPMMFDUFE CZ DFOUSJGVHBUJPO BOE XBTIFE XJUI XBUFS UIFTIJGUPGUIFEJGGSBDUJPOQFBLTUPXBSETBIJHIBOHMFNFBOTUIBU
BOE FUIBOPM CFGPSF ESJFE JO B WBDVVN PWFO BU ¡$ GPS I UIFMBUUJDFTISJOLTEVFUPUIFTVCTUJUVUJPOPG#J QN CZUIF
"DDPSEJOH UP UIF NPMBS SBUJPT PG $F#J UIF BCPWF TBNQMFT XFSF TNBMMFS $F QN 5IFTF BOBMZTFT QSPWF UIBU $F JPOT HP
OBNFEBT$F#J5F $F#J5F $F#J5F BOE$F#J5F JOUPUIFIPTUTVDDFTTGVMMZ
SFTQFDUJWFMZ1VSF#J5FXBTQSFQBSFEVOEFSUIFTBNFDPOEJUJPOT "TTIPXOJO'JH C 3BNBOTQFDUSBXFSFNFBTVSFEGPS#J5F
XJUIPVUUIFBEEJUJPOPG$F /0 r)0 BOE $F#J5F TBNQMFT GPS EFUFDUJOH UIF DSZTUBM EJTUPSUJPO 5IF
UXP QFBLT BU BOE DN¦ BSF JOEFYFE UP "V BOE AŵŴg
2.2 Synthesis of M0.3-Bi2Te3 WJCSBUJPOBM NPEFT PG #J5F XIFSF UIF i"w JOEJDBUFT UIF PVUPG
.#J5F . 'F /J $V ;S BOE "H TBNQMFT EPQFE XJUI QMBOFMBUUJDFWJCSBUJPO BOEUIFiHwBOEiVwEFOPUF3BNBOBDUJWF
EJGGFSFOUFMFNFOUTXFSFQSFQBSFE SFTQFDUJWFMZ5BLJOH'F#J5F BOEJOGSBSFEBDUJWF *3 NPEFT SFTQFDUJWFMZ<o>$PNQBSFEUP
BTBOFYBNQMF NH#J /0 r)0 NH/B5F0 NH UIF PSJHJOBM #J5F UIF QFBLT PG $F#J5F OBOPTIFFUT CFDPNF
/B0) NH 171 BOE NH 'F /0 r)0 XFSF XJEFS BOE OFHBUJWF TIJGUFE TMJHIUMZ TJHOJGZJOH BO JODSFBTF JO UIF
EJTTPMWFE JO N- PG &( BOE TUJSSFE SBQJEMZ CFGPSF CFJOH OVNCFSPGDSZTUBMEFGFDUTJO$F#J5F5IFQSPCBCMFSFBTPOGPS
USBOTGFSSFEUPBN-5FGMPOTUBJOMFTTTUFFMBVUPDMBWFBOEIFBUFE UIF CSPBEFOJOH PG UIF QFBLT JT UIF BEEJUJPOBM SFTJEVBM TUSFTTFT
BU ¡$ GPS I 5IF QSPEVDU XBT DPMMFDUFE CZ DFOUSJGVHBUJPO BQQMJFE UP UIF TVSGBDF BMPOH UIF iBBYJTw PS iCBYJTw BGUFS UIF
BOE XBTIFE XJUI XBUFS BOE FUIBOPM CFGPSF ESJFE JO B WBDVVN OBOPTIFFUT BSF TVQFSJNQPTFE <> BT TIPXO JO 'JH4 JO UIF
PWFOBU¡$GPSI0UIFSTBNQMFTXFSFQSFQBSFEBDDPSEJOHMZ &4. 5IF TIJGU JT BUUSJCVUFE UP UIF DIBOHF JO JOUFSMBZFS WBO EFS
FYDFQU UIBU NH PG 'F /0 r)0 XBT SFQMBDFE CZ 8BBMT GPSDFT CFDBVTF PG UIF EJTMPDBUJPO BTDSJCFE UP UIF MBUUJDF
NHPG/J /0 r)0 NHPG$V /0 r)0 NH NJTNBUDIBOESFTJEVBMJOUFSOBMTUSFTT< >
PG;S$M BOENHPG"H/0 SFTQFDUJWFMZ.PSFFYQFSJNFOUBM *OPSEFSUPJOWFTUJHBUFUIFDIFNJDBMDPNQPTJUJPOBOEWBMFODFPG
‫ڀ‬
www.theNanoResearch.com | www.Springer.com/journal/12274 | Nano Research

6546 Nano Res. 2023, 16(5): 6544–6551
‫ڀ‬
‫ڀ‬
'JHVSF‫ ڀڀ‬B 4&. D 5&. BOE F "'.JNBHFTPGQVSF#J5FOBOPTIFFUT C 4&. E 5&. G "'. H )""%'45&. BOE I o K &%4FMFNFOUNBQQJOH
JNBHFTPG$F#J5FOBOPTIFFUT
‫ڀ‬
2ș (°)
'JHVSF‫ ڀڀ‬B 93% QBUUFSOT PG #J5F BOE $FY#J5F C 3BNBO TQFDUSB PG #J5F BOE $F#J5F 914 TQFDUSB PG #J5F BOE $F#J5F D TVSWFZ E $F E
F #JG BOE G 5FE
UIF DBUBMZTUT UIF 9SBZ QIPUPFMFDUSPO TQFDUSPTDPQZ 914 TQFDUSB CJOEJOH FOFSHJFT #&T PG $ 0 #J 5F BOE $F JO UIF #J5F
XFSF QFSGPSNFE PO UIF #J5F BOE $F#J5F TBNQMFT 5IF OBOPTIFFUTBOE$F#J5FTBNQMFT BNPOHXIJDIUIF#&TPG0
TVSWFZ TQFDUSB 'JH D TIPX UIF QFBLT DPSSFTQPOEJOH UP UIF BOE $ DBO CF BUUSJCVUFE UP BJS FYQPTVSF BOE DBSCPO
‫ڀ‬
| www.editorialmanager.com/nare/default.asp
Nano Res. 2023, 16(5): 6544–6551 6547
‫ڀ‬
DPOUBNJOBUJPO*O'JH E UIF$FETQFDUSVNDBOCFXFMMGJUUFE TUSVDUVSF JOEJDBUFE CZ UIF CMVF EBTIFE <> #FTJEFT UIF EFGFDUT
JOUP UISFF QBJST PG TQJOPSCJU CBOET "NPOH UIFN UIF QFBLT NFOUJPOFEBCPWF PUIFSUZQFTPGEFGFDUT TVDIBTIFUFSPBUPNT BMTP
NBSLFE BT 6 F7 6h F7 6 F7 BOE 6h FYJTUJODSZTUBMTUIBUBSFOPUFBTJMZPCTFSWFEEJSFDUMZGSPN)35&.
F7 DPSSFTQPOE UP $F XIFSFBT UIPTF EFOPUFE BT 7 %VFUPUIFTZOFSHJTUJDFGGFDUPGEFGFDUT DPNCJOJOHNVMUJQMFEFGFDUT
F7 BOE 7h F7 BSF BTTJHOFE UP $F < > 5IVT DBO FGGFDUJWFMZ SFHVMBUF UIF DPOEVDUJWJUZ BOE EJTUSJCVUJPO PG
CPUI$F BOE$F FYJTUJO$F#J5F*UJTXPSUIOPUJOHUIBUUIF FMFDUSPOT PO UIF NBUFSJBMT GBDJMJUBUJOH FMFDUSPO USBOTGFS BOE UIF
QSFTFODF PG $F EJTUVSCT UIF DIBSHF CBMBODF PG UIF TZTUFN BETPSQUJPOPGJOUFSNFEJBUFTBOESFBDUBOUT< > UIVTGVSUIFS
SFTVMUJOH JO UIF HFOFSBUJPO PG WBDBODJFT GPS UIF DIBSHF DSFBUJOH DBUBMZTUT UIBU QPTTFTT B IJHI EFOTJUZ PG PQUJNJ[FE BDUJWF
DPNQFOTBUJPO< >*UJTDPOTJTUFOUXJUIUIF&%4BOE*$10&4 TJUFTBOEPVUTUBOEJOHQFSGPSNBODF
DIBSBDUFSJ[BUJPO SFTVMUT XIJDI TIPXFE UIBU UIF 5F DPOUFOU "T / DIFNJTPSQUJPO JT UIF GJSTU TUFQ UPXBSET /33 UIF /
EFWJBUFE GSPN UIF TUPJDIJPNFUSJD SBUJP XJUI UIF BEEJUJPO PG $F DIFNJTPSQUJPO BCJMJUZ PG UIF DBUBMZTUT XBT NFBTVSFE CZ
'JHVSF F TIPXT TFWFSBM QFBLT DPSSFTQPOEJOH UP #J G BOE #J UFNQFSBUVSFQSPHSBNNFE EFTPSQUJPO 51% 'JHVSF 4 JO UIF
G *O #J5F OBOPTIFFUT UIF QFBLT BU BOE F7 BSF &4.TIPXTUIBU#J5FIBTXFBL/DIFNJTPSQUJPO XIJDINBZCF
BTTPDJBUFEXJUIUIFGBOEGPSCJUBMTPG#J SFTQFDUJWFMZ XIJMF SFMBUFE UP UIF FYJTUFODF PG B GFX 5F WBDBODJFT PO UIF TVSGBDF <
UIF QFBLT BU BOE F7 BSF SFMBUFE UP UIF G BOE G >)PXFWFS UIFDBUBMZTUTTIPXBTJHOJGJDBOUFOIBODFNFOUPG/
PSCJUBMTPG#JJO$F#J5F5IFQFBLTBUBOEF7 BOE DIFNJTPSQUJPO BGUFS $F EPQJOH QBSUJDVMBSMZ GPS $F#J5F *O
BOE F7 BSF DPOTJTUFOU XJUI UIF #&T PG #J PG #J5F BEEJUJPOUPUIFFOIBODFEJOUFOTJUZ UIFQFBLTBSFBMTPTIJGUFE5IF
OBOPTIFFUT BOE $F#J5F SFTQFDUJWFMZ $PNQBSJOH UIFTF UXP /EFTPSQUJPOQFBLPG#J5FJTMPDBUFEBU¡$ XIJMFUIFQFBLPG
TQFDUSB JUJTGPVOEUIBUUIFDPOUFOUPGNFUBMMJD#JPOUIFTVSGBDFPG $F#J5FJTTIJGUFEUP¡$5IFTIJGUPGUIFQFBLUPBIJHIFS
$F#J5FEFDSFBTFTBGUFSEPQJOH*UNBZCFDBVTFECZUIFDIBSHF UFNQFSBUVSF JOEJDBUFT IJHIFS CJOEJOH FOFSHZ BOE TUSPOHFS
JNCBMBODF BGUFS UIF JOUSPEVDUJPO PG $F SFTVMUJOH JO UIF DIFNJDBM BETPSQUJPO PG HBT NPMFDVMFT < > /PUBCMZ UIF
HFOFSBUJPO PG 5F WBDBODJFT BOE VOTBUVSBUFE #J BUPNT XJUI BEEJUJPOPG$FEPFTOPUHFOFSBUFOFXQFBLT JNQMZJOHUIBUOPOFX
EBOHMJOH CPOET JO UIF NBUFSJBMT < > 5IFTF BUPNT BSF OJUSPHFO BETPSQUJPO TJUFT BSF GPSNFE BOE BMTP SVMJOH PVU UIF
FBTJMZPYJEJ[FEXIFOFYQPTFEUPBJS MFBEJOHUPBOJODSFBTFEEFHSFF QPTTJCJMJUZ PG $F BT UIF OJUSPHFO BETPSQUJPO TJUF < > 5IF
PG PYJEBUJPO < > "U UIF TBNF UJNF EVF UP UIF IJHI FOIBODFE/BETPSQUJPODBQBDJUZPGUIFDBUBMZTUTDBOCFBUUSJCVUFE
PYJEBUJPO TUBUF DBVTFE CZ UIF JODSFBTFE EBOHMJOH CPOET PG #J UPNPSFEFGFDUTBSJTJOHJOUIF#J5FDSZTUBMT$PNQBSFEUPPUIFS
BUPNT BGUFS EPQJOH UIF FMFDUSPO DMPVE EFOTJUZ BSPVOE #J BUPNT TBNQMFT UIFTUSPOHCJOEJOHPG/PO$F#J5FJOEJDBUFTUIBUUIF
EFDSFBTFT BOE UIF #J G QFBLT PG $F#J5F BSF TIJGUFE UPXBSE DBUBMZTU IBT FYDFMMFOU OJUSPHFO BETPSQUJPO DBQBCJMJUZ *U TVHHFTUT
IJHIFS#&T<>4JNJMBSMZ UIF914TQFDUSBPG5FE 'JH G BMTP UIBU UIF JOUSPEVDUJPO PG NPEFTU EFGFDUT BMMPXT UIF DBUBMZTU UP
TIPXTGPVSTFQBSBUFQFBLTJOUIF#J5FOBOPTIFFUT5IFQFBLTBU BDIJFWFPQUJNBM/BETPSQUJPOQFSGPSNBODF BOEUIVTTJHOJGJDBOUMZ
BOE F7 BSF BTTPDJBUFE XJUI 5F QSPCBCMZ SBJTFE CZ FOIBODFT/33BDUJWJUZ
TVSGBDF PYJEBUJPO XIJMF UIF QFBLT BU BOE F7 BSF
BTDSJCFEUP5F*UJTGPVOEUIBUUIFQFBLQPTJUJPOTPG5FEJO$F 3.2 Electrochemical measurements
#J5FBSFUIFTBNFBTUIPTFPG#J5FOBOPTIFFUT#VUUIFDPOUFOU 5IFFMFDUSPDBUBMZUJD/33QFSGPSNBODFPG$F#J5FXBTUFTUFEJO
PG5FTJHOJGJDBOUMZEFDSFBTFT XIJDINBZCFEVFUPJUTPYJEBUJPOCZ . /B40 BRVFPVT TPMVUJPO 5IF HBTFT XFSF TFRVFOUJBMMZ
$F PSUIFHFOFSBUJPOPG5FWBDBODJFT QVSJGJFECZ.)40TPMVUJPOBOEXBUFSUPSFNPWFQPTTJCMF
5P CFUUFS VOEFSTUBOE UIF FGGFDU PG JPO EPQJOH PO UIF /)BOE/0YCFGPSFFOUFSJOHUIFFMFDUSPMZUJDDFMM5IFQSPEVDFE
NJDSPTUSVDUVSFPGUIFNBUFSJBMT #J5FBOE$F#J5FOBOPTIFFUT /) XBT RVBOUJGJFE CZ UIF JOEPQIFOPM CMVF BOE GMVPSFTDFODF
XFSFDIBSBDUFSJ[FECZUIFIJHISFTPMVUJPO5&. )35&. 'JHVSF NFUIPE SFTQFDUJWFMZ XIJMF UIF /) DPOUFOU XBT EFUFSNJOFE CZ
4 B JOUIF&4.TIPXTUIF)35&.JNBHFPG#J5FOBOPTIFFUT UIF 8BUU BOE $ISJTQ NFUIPE 5IF DPSSFTQPOEJOH TQFDUSB BOE
5IF QSFQBSFE #J5F OBOPTIFFUT TIPX B DSZTUBM QMBOF TQBDJOH PG GJUUJOH DVSWFT BSF TIPXO JO 'JHT 4o4 JO UIF &4. SFTQFDUJWFMZ
ON XIJDIJTDPOTJTUFOUXJUIUIFEWBMVFPGUIF QMBOF 'JHVSF B TIPXT UIF MJOFBS TXFFQ WPMUBNNFUSZ -47 DVSWFT PG
PG#J5F*OBEEJUJPO UIFJNBHFQSPDFTTFECZBQQMZJOHUIFNBTL $F#J5F JO "S PS /TBUVSBUFE FMFDUSPMZUF *U JT DMFBS UIBU UIF
PG UIF QMBOF TIPXT UIF MBUUJDF EFGFDUT PG #J5F DPVME CF DVSSFOU EFOTJUZ PG $F#J5F JO UIF / BUNPTQIFSF JT IJHIFS
TFMEPN GPVOE CFGPSF JPO EPQJOH JOTFU 'JH4 B JO UIF &4. SFWFBMJOHUIFQPTJUJWFSFTQPOTFUP/335IFDISPOPBNQFSPNFUSJD
'VSUIFSNPSF UIFTFMFDUFEBSFBFMFDUSPOEJGGSBDUJPO 4"&% QBUUFSO DVSWFTPG$F#J5FBUEJGGFSFOUQPUFOUJBMTBSFTIPXOJO'JH C
PG SFHVMBSMZ EJTUSJCVUFE EJTDSFUF EPUT SFWFBMT UIBU UIF TZOUIFTJ[FE 5IFDPSSFTQPOEJOHVMUSBWJPMFUoWJTJCMF 67oWJT TQFDUSBBSFTIPXO
#J5FOBOPTIFFUTIBWFUIFFYDFMMFOUDSZTUBMMJOJUZ JOTFU 'JH4 B JO'JH D 5IFIJHIFTU/)ZJFME ϪHrI¦rNHDBU¦ BOEMBSHFTU
JOUIF&4. 'JHVSF4 C JOUIF&4.TIPXTUIF)35&.JNBHFPG '& BSF BDIJFWFE BU ¦ 7 BT TIPXO JO 'JH E BOE
$F#J5F $F#J5F OBOPTIFFUT IBWF B DSZTUBM QMBOF TQBDJOH 5BCMF4JOUIF&4.5IJTSFTVMUJTTVQFSJPSUPNPTUPGUIF$FBOE
PG ON XIJDI NBUDIFT XFMM XJUI UIF QMBOF 5IF #JCBTFEDBUBMZTUTUIBUIBWFCFFOSFQPSUFEGPS/33JOUIFBRVFPVT
EJGGFSFODF JO UIF DSZTUBM QMBOF TQBDJOH SFTVMUT GSPN UIF TMJHIU TPMVUJPO 5BCMF4JOUIF&4. "GUFSUIBU UIFZJFMEBOE'&CPUI
QFSUVSCBUJPOPG#J5FCZ$FEPQJOH XIJDIJTDPOTJTUFOUXJUIUIF EFDSFBTF XIFO UIF BQQMJFE QPUFOUJBMT CFDPNF OFHBUJWF PXJOH UP
93% SFTVMUT .FBOXIJMF UIF QSPDFTTFE JNBHF CZ BQQMZJOH UIF UIFSBQJEMZJODSFBTJOH)&3DPNQFUJUJPO< >'VSUIFSNPSF UIF
NBTLPGUIF QMBOFTIPXTUIBUMBUUJDFEJTUPSUJPOTBSFGPSNFE BNNPOJB ZJFMET BU EJGGFSFOU QPUFOUJBMT XFSF BMTP EFUFDUFE CZ UIF
JO$F#J5F JOTFU 'JH4 C JOUIF&4. .PSFPWFS JUDBOCF GMVPSFTDFODF NFUIPE BT TIPXO JO 'JH4 B JO UIF &4. 'JHVSF
TFFOGSPNUIF4"&%JNBHFPG$F#J5FUIBUUIFDSZTUBMMJOJUZPG 4 C JO UIF &4. TIPXT UIBU UIF OFHMJHJCMF EJGGFSFODF PG /)
UIFOBOPTIFFUTEFDSFBTFTBGUFS$FEPQJOH JOTFU 'JH4 C JOUIF DPOUFOUEFUFDUFECZUIFUXPNFUIPET QSPWJOHUIFIJHISFMJBCJMJUZ
&4. XIJDI JT BTTPDJBUFE XJUI UIF BQQFBSBODF PG EFGFDUT 'JHVSF PG UIF /) RVBOUJUBUJWF BOBMZTJT *O BEEJUJPO /) XBT OPU
4 D JOUIF&4.TIPXTTFWFSBMEJGGFSFOUUZQFTPGEFGFDUTBQQFBSJOH EFUFDUFE BU BMM BQQMJFE WPMUBHFT 'JH4 JO UIF &4. JOEJDBUJOH
PO $F#J5F TVDI BT QPJOU EFGFDUT BSFBT DJSDMFE CZ UIF SFE UIF FYDFMMFOU TFMFDUJWJUZ PG $F#J5F GPS /) TZOUIFTJT
EBTIFE TVSGBDFWBDBODZEFGFDUTXJUIIJHIEFOTJUZ BSFBTFODMPTFE .PSFPWFS UIF /33 QFSGPSNBODF PG $F#J5F XBT BMTP
CZ UIF HSFFO EBTIFE BOE EJTMPDBUJPOT BSFBT NBSLFE CZ UIF FWBMVBUFE JO . )$M BOE . ,0) TPMVUJPO SFTQFDUJWFMZ
ZFMMPX EBTIFE *O BEEJUJPO JU JT BMTP QPTTJCMF UP PCTFSWF UIF BOE MPXFS /) ZJFME SBUFT BOE TNBMMFS '&T XFSF PCUBJOFE JO UIF
JOUFSGBDF CFUXFFO UIF DSZTUBM TUSVDUVSF BOE UIF BNPSQIPVT BCPWFFMFDUSPMZUFTDPNQBSFEUP./B40TPMVUJPO 'JH4JO
‫ڀ‬

6548 Nano Res. 2023, 16(5): 6544–6551
‫ڀ‬
‫ڀ‬
Chemical shift (ppm)

'JHVSF‫ ڀڀ‬B -47DVSWFTPG$F#J5FJO"SPS/TBUVSBUFE./B40TPMVUJPOXJUIBTDBOSBUFPGN7rT C $ISPOPBNQFSPNFUSJDDVSWFTPG$F#J5FBU
¦
EJGGFSFOUQPUFOUJBMTJO/TBUVSBUFE./B40TPMVUJPO D 67oWJTTQFDUSBPGUIFFMFDUSPMZUFBGUFSFMFDUSPMZTJTBUUIFDPSSFTQPOEJOHQPUFOUJBMTGPSI E /)ZJFME

SBUFT BOE '&T PG $F#J5F BU FBDI HJWFO QPUFOUJBMT F /) ZJFME SBUFT BOE '&T PG #J5F BOE $FY#J5F BU ¦ 7 G )/.3 TQFDUSB PG TPMVUJPO BGUFS
FMFDUSPDBUBMZUJD/33VTJOH$F#J5FBTUIFFMFDUSPDBUBMZTUJO/PS/BUNPTQIFSF
UIF&4. SFTVMUJOHGSPNUIFTIBSQMZQSPNPUFEDPNQFUJUJWF)&3 TVCTUSBUFBOEUIFEPQJOHFMFNFOUJTUIFDPSFPGUIFEPQJOHTUSBUFHZ

<o> < >
6OEFS UIF TJNJMBS DPOEJUJPOT /33 UFTUT XFSF DBSSJFE PVU GPS 5P WFSJGZ UIF PSJHJO PG HFOFSBUFE BNNPOJB JTPUPQJD MBCFMJOH
PUIFS $FEPQFE TBNQMFT *U JT DMFBS UIBU UIF $F#J5F FYQFSJNFOUT XFSF DPOEVDUFE VTJOH / "OE UIF QSPEVDU XBT
OBOPTIFFUTIBWFUIFIJHIFTUBNNPOJBZJFMEBOE'& 'JH F BOE NFBTVSFE CZ UIF ) OVDMFBS NBHOFUJD SFTPOBODF /.3
5BCMF4JOUIF&4. 5IJTSFTVMUJOEJDBUFTUIBU DPNQBSFEUPPUIFS TQFDUSPTDPQZ"TTIPXOJO'JH G UIF )/.3TQFDUSBSFWFBMB
TBNQMFT UIF /33 QFSGPSNBODF PG UIF #J5F OBOPTIFFUT JT EPVCMFUDPVQMJOHGPS /) BOEBUSJQMFUDPVQMJOHGPS /) XJUI
PQUJNJ[FECZUIFDPOTUSVDUJPOPGUIFNPEFSBUFBNPVOUPGDSZTUBM
/ BOE / BT GFFEJOH HBT NBUDIJOH UP UIF TQFDUSB PG UIFJS
EFGFDUT BU UIJT EPQJOH SBUJP )PXFWFS B MBSHFS BNPVOU PG EFGFDUT TUBOEBSE TVCTUBODFT SFTQFDUJWFMZ < > XIJDI JNQMJFT UIBU UIF
CZNPSF$FEPQJOHNBZMFBEUPUIFQPPSTUBCJMJUZPGUIFNBUFSJBMT QSPEVDFE/)‫ڀ‬JTGSPN/33PG$F#J5F.PSFPWFS GPVSFYUSB
"T TIPXO JO 'JH4 JO UIF &4. JU JT GPVOE UIBU UIF DVSSFOU DPOUSPM FYQFSJNFOUT XFSF QFSGPSNFE <> UIF BCTPSCBODF PG
EFOTJUZ PG $F#J5F OBOPTIFFUT GMVDUVBUFT TJHOJGJDBOUMZ EVSJOH GSFTIFMFDUSPMZUFBTBCMBOLDPOUSPM $F#J5FJO/TBUVSBUFE
UIFMPOHUFSNTUBCJMJUZUFTU BOEUIFJSQPPSTUBCJMJUZNBZSFEVDFUIF ./B40TPMVUJPOBUBOPQFODJSDVJUQPUFOUJBM 0$1 GPSI
DBUBMZUJD BDUJWJUZ PG UIF NBUFSJBMT 5IFSFGPSF JU JT TJHOJGJDBOU UP $F#J5FJO"STBUVSBUFE./B40TPMVUJPOBU¦7
SFHVMBUFUIFDPODFOUSBUJPOPGEFGFDUTUPJNQSPWFUIFQFSGPSNBODF GPS I BOE B CBSF HMBTTZ DBSCPO FMFDUSPEF ($& JO /
PGUIFDBUBMZTUT<> TBUVSBUFE./B40TPMVUJPOBU¦7GPSI5IFSFXBTOP
.FBOXIJMF UPJOWFTUJHBUFUIFFGGFDUPGEPQJOHFMFNFOUTPOUIF PCWJPVT BNNPOJB EFUFDUFE JO UIF BCPWF DPOUSPM FYQFSJNFOUT BT
QFSGPSNBODFPG#J5FOBOPTIFFUT /33UFTUTXFSFQFSGPSNFEPO TIPXO JO 'JH4 JO UIF &4. XIJDI JOEJDBUFE UIBU /
UIF TBNQMFT PG .#J5F . 'F /J $V ;S BOE "H GPS DPOUBNJOBUJPO PG PVS FMFDUSPDIFNJDBM UFTU TZTUFN XBT OFHMJHJCMF
DPNQBSJTPO 'JSTUMZ UIF DPNQPTJUJPO PG UIFTF TBNQMFT XBT BOE UIF EFUFDUFE /) EJE PSJHJOBUF GSPN UIF FMFDUSPDIFNJDBM
BOBMZ[FECZ&%4BOE*$10&4 SFTQFDUJWFMZ 'JH4BOE5BCMFT SFEVDUJPOPG/PO$F#J5F
4 BOE 4 JO UIF &4. 'JHVSF 4 B JO UIF &4. EFQJDUT UIF 5P FWBMVBUF UIF DIBSHF USBOTGFS BCJMJUZ PG FMFDUSPDBUBMZUJD
OPSNBMJ[FE 93% QBUUFSOT PG BMM UIF TZOUIFTJ[FE .#J5F
NBUFSJBMT UIF FMFDUSPDIFNJDBM JNQFOEFODF TQFDUSPTDPQZ &*4 PG
OBOPTIFFUT %FTQJUF UIF EPQJOH PG JPOT JO #J5F B TJOHMFQIBTF
UIFTBNQMFTXBTSFDPSEFE'JHVSF4JOUIF&4.TIPXTUIBUXJUI
#J5F JT GPSNFE XJUI BMM EJGGSBDUJPO QFBLT DMFBSMZ JOEFYFE UP UIF
UIF JODSFBTF JO $F DPOUFOU UIF JNQFEBODF BSD EJBNFUFS PG UIF
SIPNCPIFESBM#J5F 1%' )PXFWFS JOUIFNBHOJGJFE
TBNQMFT HSBEVBMMZ EFDSFBTFT JOEJDBUJOH UIBU UIF DIBSHF USBOTGFS
93% JNBHF 'JH4 C JO UIF &4. UIF QSJNBSZ QFBLT PG UIF
TBNQMFTBSFEJTQMBDFEUPEJGGFSFOUEFHSFFTBOEEJSFDUJPOT XIJDIJT SFTJTUBODF CFDPNFT TNBMMFS *U SFTVMUT GSPN UIF GBTU FMFDUSPO
EVFUPUIFWBSZJOHTJ[FTPGUIFEPQBOUJPOT< >'JHVSF4JO USBOTGFSQBUIQSPWJEFECZUIFNVMUJWBMFOU$FJPOT< > BTXFMM
UIF &4. EJTQMBZT UIF OPSNBMJ[FE 3BNBO TQFDUSB PG .#J5F BTUIFDSZTUBMEFGFDUTQSPNPUJOHJOUFSGBDJBMDIBSHFUSBOTGFSCFUXFFO
BOE BMM PG UIF TBNQMFT FYIJCJU UIF UZQJDBM WJCSBUJPO NPEFT PG UIFDBUBMZTUTBOEUIFBETPSCFENPMFDVMFT<>5PGVSUIFSFMVDJEBUF
#J5F 5IJT NFBOT UIBU UIF EPQJOH PG EJGGFSFOU JPOT IBT OP UIFFOIBODFNFOUPG/33QFSGPSNBODF UIFFMFDUSPDIFNJDBMBDUJWF
TJHOJGJDBOU BMUFSBUJPO UP UIF DIFNJDBM TUSVDUVSF 0UIFSXJTF UIF TVSGBDF BSFB &$4" PG UIF NBUFSJBMT XBT DBMDVMBUFE BDDPSEJOH UP
3BNBO QFBL QPTJUJPO XPVME CF DIBOHFE SFNBSLBCMZ BOE OFX UIF FMFDUSPDIFNJDBM EPVCMF MBZFS DBQBDJUBODF $EM 'JHVSF 4 JO
QFBLT XPVME TIPX VQ JO UIF EPQFE TBNQMFT < > 5IFO UIF &4. TIPXT UIBU $F#J5F OBOPTIFFUT IBWF UIF MBSHFTU $EM
BDDPSEJOHUPUIFQSFWJPVTUFTUQSPDFEVSF /33UFTUTXFSFDBSSJFE WBMVFBNPOHUIFTFTBNQMFT JNQMZJOHUIBUUIFZQPTTFTTUIFMBSHFTU
PVU PO UIF GJWF TBNQMFT VOEFS UIF TBNF UFTU DPOEJUJPOT 5IF UFTU &$4" BOE UFOE UP FYQPTF NPSF BDUJWF TJUFT XIJDI JT DPOTJTUFOU
SFTVMUTBSFTIPXOJO'JH4BOE5BCMF4JOUIF&4.*UDBOCF XJUI UIF /51% SFTVMUT 5IF IJHIFTU DBUBMZUJD BDUJWJUZ PG $F
TFFOUIBUUIFEPQJOHFGGFDUPG$FFMFNFOUBDIJFWFTUIFCFTUDBUBMZUJD #J5FQSPCBCMZBSJTFTGSPNBOPQUJNJ[FETUBUFPGNVMUJQMFEFGFDUT
QFSGPSNBODF XIJDI QSPWFT UIBU UIF NBUDIJOH CFUXFFO UIF XIJDISFTVMUTJOUIFMBSHFTUJOUFSGBDJBMBSFBBOEUIFCFTUBETPSQUJPO
‫ڀ‬
Nano Res. 2023, 16(5): 6544–6551 6549
‫ڀ‬
QFSGPSNBODF UIFSFGPSF NBYJNJ[FT UIF DBUBMZUJD BDUJWJUZ $F $F#J5F XBT UFTUFE CZ DPOUJOVPVT DZDMFT PG FMFDUSPMZTJT BU
#J5FXJUIBOFYDFTTPGEFGFDUTTIPXTBCJUMPXFSBDUJWJUZ CVUTUJMM ¦ 7 'JH C "GUFS TJY TVDDFTTJWF DZDMFT /) ZJFME
NVDI IJHIFS UIBO UIF QSJTUJOF #J5F QSPCBCMZ CFDBVTF BO NBJOUBJOFE BU BOE '& SFNBJOFE BU PG UIF PSJHJOBM
FYDFTTJWFJODSFBTFJOUIFEFHSFFPGEFGFDUTMFBETUPBEFDSFBTFJOUIF SFTQFDUJWFMZ 'JH D *O BEEJUJPO UIF ZJFME PG /) SPTF XJUI
JOUFSGBDJBMBSFBBOEBIJHIMFWFMPGTUSVDUVSBMJOTUBCJMJUZ5IFSFGPSF JODSFBTJOH FMFDUSPMZTJT UJNF "GUFS I PG DPOUJOVPVT FMFDUSPMZTJT
UIF SBUJPOBM EFTJHO BOE DPOUSPM PG EFGFDU UZQF BOE DPOUFOU JT UIFUPUBMBNNPOJBQSPEVDUJPOXBTPGUIFUIFPSFUJDBMWBMVF
FTTFOUJBMGPSUIFFYQMPSBUJPOPGBEWBODFEDBUBMZTUT 'JH E 'VSUIFSNPSF JU XBT DPOGJSNFE CZ 914 BOBMZTJT UIBU
4UBCJMJUZJTBLFZBTQFDUUPCFFWBMVBUFEJOQSBDUJDBMBQQMJDBUJPOT BGUFS UIF DBUBMZUJD SFBDUJPO POMZ UIF DPOUFOU PG 5F JODSFBTFE
$F#J5FXBTUFTUFEBU¦7GPSIXJUIDPOTUBOUDVSSFOU TMJHIUMZ BOE PUIFS DIFNJDBM DPNQPOFOUT SFNBJOFE CBTJDBMMZ
EFOTJUZ 'JH B 5IFJOTFUPG'JH B TIPXTUIFDPNQBSJTPOPG VODIBOHFE 'JH4 JO UIF &4. 93% BOBMZTJT DPOGJSNFE OP
/) ZJFME BOE '& PG UIF DBUBMZTU BGUFS FMFDUSPMZTJT GPS I BU TJHOJGJDBOUDIBOHFTJOUIFQSPQFSUJFTPG$F#J5F 'JH4JOUIF
¦ 7 XJUI UIF WBMVFT SFNBJOJOH BSPVOE BOE PG &4. BOE 4&. DIBSBDUFSJ[BUJPO SFTVMU EFNPOTUSBUFE UIF
UIF PSJHJOBM SFTQFDUJWFMZ #Z *$10&4 BOBMZTJT OP TJHOJGJDBOU SFUFOUJPO PG UIF IFYBHPOBM NPSQIPMPHZ PG UIF DBUBMZTU BGUFS /33
MFBDIJOH PG UIF TBNQMF JOUP UIF FMFDUSPMZUF XBT PCTFSWFE 'JH4 JO UIF &4. "MM PG UIF UFTUT FGGFDUJWFMZ EFNPOTUSBUFUIF
XU BGUFSFMFDUSPMZTJTGPSI*OBEEJUJPO UIFTUBCJMJUZPG FYDFMMFOUTUBCJMJUZPG$F#J5F
‫ڀ‬
‫ڀ‬
'JHVSF‫ ڀڀ‬B -POHUJNF DISPOPBNQFSPNFUSJD NFBTVSFNFOU PG $F#J5F BU ¦ 7 C $ISPOPBNQFSPNFUSJD SFTQPOTF PG $F#J5F BU ¦ 7 GPS TJY
DPOUJOVPVTDZDMFT FBDIGPSI D /)ZJFMETBOE'&TPG$F#J5FEVSJOHTJYSFDZDMJOHUFTUTBU¦7JO/TBUVSBUFE./B40TPMVUJPO E /)ZJFMETPG
$F#J5FBU¦7GSPNUPI
‫ڀ‬
‫ڀڀڀڀ‬$PODMVTJPOT
‫ڀ‬
&MFDUSPOJD 4VQQMFNFOUBSZ .BUFSJBM‫ڀڀ‬4VQQMFNFOUBSZ NBUFSJBM
‫ڀ‬
GVSUIFS EFUBJMT PG UIF FYQFSJNFOUBM TFDUJPO DPSSFTQPOEJOH

*O TVNNBSZ XF SFQPSUFE B HFOFSBM TUSBUFHZ UP FOHJOFFS BOE DBMJCSBUJPO DVSWFT DPOUSPM FYQFSJNFOU FMFDUSPDIFNJDBM
GBCSJDBUFDSZTUBMEFGFDUTCZ$FEPQJOHUPJNQSPWFUIF/33BDUJWJUZ NFBTVSFNFOU PG DPOUSBTU NBUFSJBMT /) EFUFSNJOBUJPO &*4
PG #J5F OBOPTIFFUT #Z DIBOHJOH UIF EPQBOU DPOUFOU DSZTUBM 4&. 93% 914 DIBSBDUFSJ[BUJPOT BOE TP PO JT BWBJMBCMF JO UIF
EFGFDUT DPVME CF EFTJHOFE BOE DPOUSPMMFE CZ NFBOT PG JPO POMJOFWFSTJPOPGUIJTBSUJDMFBUIUUQTEPJPSHT
TVCTUJUVUJPO BOE DIBSHF DPNQFOTBUJPO 5IF XFMMFOHJOFFSFE Y
DSZTUBM EFGFDUT XFSF QSPWFE UP BDIJFWF FOIBODFE /33 BDUJWJUZ CZ
JODSFBTJOH UIF FMFDUSPDIFNJDBM BDUJWF BSFB PG UIF TVCTUSBUFT BOE 3FGFSFODFT ‫ڀ‬
SFEVDJOH UIF JNQFEBODF PG UIF NBUFSJBMT $PNQBSFE UP QSJTUJOF

[1] Soloveichik, G. Electrochemical synthesis of ammonia as a potential
#J5F $F#J5FFYIJCJUFEBIJHI/)ZJFMEPGϪHrI¦rNHDBU¦ ‫ڀ‬
alternative to the Haber–Bosch process. Nat. Catal. 2019, 2,

BOE B IJHI '& PG BU ¦ 7 JO . /B40 TPMVUJPO
377–380.
/PUBCMZ JUBMTPQPTTFTTFEFYDFMMFOUTUSVDUVSBMBOEFMFDUSPDIFNJDBM [2] Liang, J.; Liu, P. Y.; Li, Q. Y.; Li, T. S.; Yue, L. C.; Luo, Y. S.; Liu,
EVSBCJMJUZ 5IJT XPSL OPU POMZ QSPWJEFT B GBDJMF TUSBUFHZ GPS
‫ڀ‬
Q.; Li, N.; Tang, B.; Alshehri, A. A. et al. Amorphous boron carbide
FOIBODJOH UIF /33 QFSGPSNBODF PG #J5F OBOPTIFFUT CVU BMTP on titanium dioxide nanobelt arrays for high-efficiency
QSPWJEFT B SFMJBCMF BQQSPBDI GPS EFTJHOJOH BOE GBCSJDBUJOH UXP electrocatalytic NO reduction to NH3. Angew. Chem., Int. Ed. 2022,
EJNFOTJPOBMMBZFSFEOBOPNBUFSJBMTXJUIUVOBCMFDSZTUBMEFGFDUTGPS 61, e202202087.
BSUJGJDJBM/GJYBUJPO [3] Deng, J.; Iñiguez, J. A.; Liu, C. Electrocatalytic nitrogen reduction at
‫ڀ‬
low temperature. Joule 2018, 2, 846–856.

"DLOPXMFEHFNFOUT
‫ڀ‬
[4] Li, S. X.; Luo, Y. L.; Yue, L. C.; Li, T. S.; Wang, Y.; Liu, Q.; Cui,
‫ڀ‬
G. W.; Zhang, F.; Asiri, A. M.; Sun, X. P. An amorphous WC thin

5IJT XPSL XBT GJOBODJBMMZ TVQQPSUFE CZ UIF /BUJPOBM /BUVSBM film enabled high-efficiency N2 reduction electrocatalysis under
4DJFODF'PVOEBUJPOPG$IJOB /PTBOE ambient conditions. Chem. Commun. 2021, 57, 7806–7809.
‫ڀ‬

6550 Nano Res. 2023, 16(5): 6544–6551
‫ڀ‬
[5] Chen, X. Z.; Li, N.; Kong, Z. Z.; Ong, W. J.; Zhao, X. J.
‫ڀ‬
[24] Jo, W. J.; Jang, J. W.; Kong, K. J.; Kang, H. J.; Kim, J. Y.; Jun, H.;
‫ڀ‬
Photocatalytic fixation of nitrogen to ammonia: State-of-the-art Parmar, K. P. S.; Lee, J. S. Phosphate doping into monoclinic BiVO4
advancements and future prospects. Mater. Horiz. 2018, 5, 9–27. for enhanced photoelectrochemical water oxidation activity. Angew.
[6] Wen, G. L.; Liang, J.; Liu, Q.; Li, T. S.; An, X.; Zhang, F.; Alshehri,
‫ڀ‬
Chem., Int. Ed. 2012, 51, 3147–3151.

A. A.; Alzahrani, K. A.; Luo, Y. L.; Kong, Q. Q. et al. Ambient [25] Lei, F. C.; Zhang, L.; Sun, Y. F.; Liang, L.; Liu, K. T.; Xu, J. Q.;
‫ڀ‬
ammonia production via electrocatalytic nitrite reduction catalyzed Zhang, Q.; Pan, B. C.; Luo, Y.; Xie, Y. Atomic-layer-confined
by a CoP nanoarray. Nano Res. 2022, 15, 972–977. doping for atomic-level insights into visible-light water splitting.
[7] Cui, X. Y.; Tang, C.; Zhang, Q. A review of electrocatalytic
‫ڀ‬
Angew. Chem., Int. Ed. 2015, 54, 9266–9270.

reduction of dinitrogen to ammonia under ambient conditions. Adv. [26] Sun, D. D.; Zhang, G. J.; Li, D.; Liu, S. T.; Jia, X. L.; Zhou, J. S. A
Energy Mater. 2018, 8, 1800369.
‫ڀ‬
layered Bi2Te3 nanoplates/graphene composite with high gravimetric

[8] Xue, X. L.; Chen, R. P.; Yan, C. Z.; Zhao, P. Y.; Hu, Y.; Zhang, W.
and volumetric performance for Na-ion storage. Sustainable Energy
‫ڀ‬
J.; Yang, S. Y.; Jin, Z. Review on photocatalytic and electrocatalytic

Fuels 2019, 3, 3163–3171.
artificial nitrogen fixation for ammonia synthesis at mild conditions:
[27] Min, Y.; Park, G.; Kim, B.; Giri, A.; Zeng, J.; Roh, J. W.; Kim, S. I.;
Advances, challenges and perspectives. Nano Res. 2019, 12,
‫ڀ‬
1229–1249. Lee, K. H.; Jeong, U. Synthesis of multishell nanoplates by

[9] Ma, B. Y.; Zhao, H. T.; Li, T. S.; Liu, Q.; Luo, Y. S.; Li, C. B.; Lu, consecutive epitaxial growth of Bi2Se3 and Bi2Te3 nanoplates and
enhanced thermoelectric properties. ACS Nano 2015, 9, 6843–6853.
‫ڀ‬
S. Y.; Asiri, A. M.; Ma, D. W.; Sun, X. P. Iron-group

electrocatalysts for ambient nitrogen reduction reaction in aqueous [28] Zhang, N.; Zheng, F. F.; Huang, B. L.; Ji, Y. J.; Shao, Q.; Li, Y. Y.;
‫ڀ‬
media. Nano Res. 2021, 14, 555–569. Xiao, X. H.; Huang, X. Q. Exploring Bi2Te3 nanoplates as versatile
[10] Mehta, P.; Barboun, P.; Herrera, F. A.; Kim, J.; Rumbach, P.; Go, D.
‫ڀ‬
catalysts for electrochemical reduction of small molecules. Adv.
B.; Hicks, J. C.; Schneider, W. F. Overcoming ammonia synthesis Mater. 2020, 32, 1906477.
scaling relations with plasma-enabled catalysis. Nat. Catal. 2018, 1, [29] Liu, M.; Yin, S. L.; Ren, T. L.; Xu, Y.; Wang, Z. Q.; Li, X. N.;
‫ڀ‬
269–275. Wang, L.; Wang, H. J. Two-dimensional heterojunction

[11] Cao, N.; Chen, Z.; Zang, K. T.; Xu, J.; Zhong, J.; Luo, J.; Xu, X.;
‫ڀ‬
electrocatalyst: Au-Bi2Te3 nanosheets for electrochemical ammonia
Zheng, G. F. Doping strain induced Bi-Ti3+ pairs for efficient N2 synthesis. ACS Appl. Mater. Interfaces 2021, 13, 47458–47464.
activation and electrocatalytic fixation. Nat. Commun. 2019, [30] Wang, Q. T.; Cui, K.; Li, J.; Wu, Y. X.; Yang, Y. X.; Zhou, X. Z.;
‫ڀ‬
10, 2877. Ma, G. F.; Yang, Z. W.; Lei, Z. Q.; Ren, S. F. Iron ion irradiated
[12] Liu, Q.; Xu, T.; Luo, Y. L.; Kong, Q. Q.; Li, T. S.; Lu, S. Y.;
‫ڀ‬
Bi2Te3 nanosheets with defects and regulated hydrophilicity to
Alshehri, A. A.; Alzahrani, K. A.; Sun, X. P. Recent advances in enhance the hydrogen evolution reaction. Nanoscale 2020, 12,
strategies for highly selective electrocatalytic N2 reduction toward 16208–16214.
ambient NH3 synthesis. Curr. Opin. Electrochem. 2021, 29, 100766. [31] Qu, Q.; Liu, B.; Liang, J.; Li, H.; Wang, J. N.; Pan, D.; Sou, I. K.
‫ڀ‬
[13] Xu, T.; Liang, J.; Wang, Y. Y.; Li, S. X.; Du, Z. B.; Li, T. S.; Liu,
‫ڀ‬
Expediting hydrogen evolution through topological surface states on
Q.; Luo, Y. L.; Zhang, F.; Shi, X. F. et al. Enhancing electrocatalytic Bi2Te3. ACS Catal. 2020, 10, 2656–2666.
N2-to-NH3 fixation by suppressing hydrogen evolution with [32] Wu, T. W.; Zhu, X. J.; Xing, Z.; Mou, S. Y.; Li, C. B.; Qiao, Y. X.;
‫ڀ‬
alkylthiols modified Fe3P nanoarrays. Nano Res. 2022, 15, Liu, Q.; Luo, Y. L.; Shi, X. F.; Zhang, Y. N. et al. Greatly improving
1039–1046. electrochemical N2 reduction over TiO2 nanoparticles by iron
[14] Zhao, Y. X.; Zhao, Y. F.; Shi, R.; Wang, B.; Waterhouse, G. I. N.;
‫ڀ‬
doping. Angew. Chem., Int. Ed. 2019, 58, 18449–18453.
Wu, L. Z.; Tung, C. H.; Zhang, T. R. Tuning oxygen vacancies in [33] Xie, H. T.; Wang, H. B.; Geng, Q.; Xing, Z.; Wang, W.; Chen, J. Y.;
‫ڀ‬
ultrathin TiO2 nanosheets to boost photocatalytic nitrogen fixation Ji, L.; Chang, L.; Wang, Z. M.; Mao, J. Oxygen vacancies of Cr-
up to 700 nm. Adv. Mater. 2019, 31, 1806482. doped CeO2 nanorods that efficiently enhance the performance of
[15] Tao, H. C.; Choi, C.; Ding, L. X.; Jiang, Z.; Han, Z. S.; Jia, M. W.;
‫ڀ‬
electrocatalytic N2 fixation to NH3 under ambient conditions. Inorg.
Fan, Q.; Gao, Y. N.; Wang, H. H.; Robertson, A. W. et al. Nitrogen Chem. 2019, 58, 5423–5427.
fixation by Ru single-atom electrocatalytic reduction. Chem 2019, 5, [34] Xu, B.; Xia, L.; Zhou, F. L.; Zhao, R. H.; Chen, H. Y.; Wang, T.;
‫ڀ‬
204–214. Zhou, Q.; Liu, Q.; Cui, G. W.; Xiong, X. L. et al. Enhancing
[16] Lv, C. D.; Qian, Y. M.; Yan, C. S.; Ding, Y.; Liu, Y. Y.; Chen, G.;
‫ڀ‬
electrocatalytic N2 reduction to NH3 by CeO2 nanorod with oxygen
Yu, G. H. Defect engineering metal-free polymeric carbon nitride vacancies. ACS Sustainable Chem. Eng. 2019, 7, 2889–2893.
electrocatalyst for effective nitrogen fixation under ambient [35] Yang, X. T.; Ma, Y. F.; Liu, Y.; Wang, K. K.; Wang, Y. Q.; Liu, M.;
‫ڀ‬
conditions. Angew. Chem., Int. Ed. 2018, 57, 10246–10250. Qiu, X. Q.; Li, W. Z.; Li, J. Defect-induced Ce-doped Bi2WO6 for
[17] Liu, C. W.; Li, Q. Y.; Wu, C. Z.; Zhang, J.; Jin, Y. G.; MacFarlane,
‫ڀ‬
efficient electrocatalytic N2 reduction. ACS Appl. Mater. Interfaces
D. R.; Sun, C. H. Single-boron catalysts for nitrogen reduction 2021, 13, 19864–19872.
reaction. J. Am. Chem. Soc. 2019, 141, 2884–2888. [36] Xu, Y. B.; Ren, Z. M.; Ren, W. L.; Cao, G. H.; Deng, K.; Zhong, Y.
‫ڀ‬
[18] Ling, C. Y.; Niu, X. H.; Li, Q.; Du, A. J.; Wang, J. L. Metal-free
‫ڀ‬
B. Hydrothermal synthesis of single-crystalline Bi2Te3 nanoplates.
single atom catalyst for N2 fixation driven by visible light. J. Am. Mater. Lett. 2008, 62, 4273–4276.
Chem. Soc. 2018, 140, 14161–14168. [37] Musah, J. D.; Guo, C.; Novitskii, A.; Serhiienko, I.; Adesina, A. E.;
‫ڀ‬
[19] Zhao, D. L.; Liang, J.; Li, J.; Zhang, L. C.; Dong, K.; Yue, L. C.;
‫ڀ‬
Khovaylo, V.; Wu, C. M. L.; Zapien, J. A.; Roy, V. A. L. Ultralow
Luo, Y. S.; Ren, Y. C.; Liu, Q.; Hamdy, M. S. et al. A TiO2−x thermal conductivity in dual-doped n-type Bi2Te3 material for
nanobelt array with oxygen vacancies: An efficient electrocatalyst enhanced thermoelectric properties. Adv. Electron. Mater. 2021,
toward nitrite conversion to ammonia. Chem. Commun. 2022, 58, 7, 2000910.
3669–3672. [38] Shahil, K. M. F.; Hossain, M. Z.; Teweldebrhan, D.; Balandin, A. A.
‫ڀ‬
[20] Tong, Y. Y.; Guo, H. P.; Liu, D. L.; Yan, X.; Su, P. P.; Liang, J.;
‫ڀ‬
Crystal symmetry breaking in few-quintuple Bi2Te3 films:
Zhou, S.; Liu, J.; Lu, G. Q.; Dou, S. X. Vacancy engineering of iron- Applications in nanometrology of topological insulators. Appl. Phys.
doped W18O49 nanoreactors for low-barrier electrochemical nitrogen Lett. 2010, 96, 153103.
reduction. Angew. Chem., Int. Ed. 2020, 59, 7356–7361. [39] Li, D.; Qin, X. Y.; Liu, Y. F.; Wang, N. N.; Song, C. J.; Sun, R. R.
‫ڀ‬
[21] Zhang, L. L.; Cong, M. Y.; Ding, X.; Jin, Y.; Xu, F. F.; Wang, Y.;
‫ڀ‬
Improved thermoelectric properties for solution grown Bi2Te3−xSex
Chen, L.; Zhang, L. X. A Janus Fe-SnO2 catalyst that enables nanoplatelet composites. RSC Adv. 2013, 3, 2632–2638.
bifunctional electrochemical nitrogen fixation. Angew. Chem., Int. [40] Qi, X.; Ma, W. G.; Zhang, X.; Zhang, C. Raman characterization and
‫ڀ‬
Ed. 2020, 59, 10888–10893. transport properties of morphology-dependent two-dimensional

[22] Sun, T.; Zhang, G. Q.; Xu, D.; Lian, X.; Li, H. X.; Chen, W.; Su, C.
‫ڀ‬
Bi2Te3 nanofilms. Appl. Surf. Sci. 2018, 457, 41–48.
L. Defect chemistry in 2D materials for electrocatalysis. Mater. [41] Liu, P. X.; Jing, P.; Xu, X.; Liu, B. C.; Zhang, J. Structural
‫ڀ‬
Today Energy 2019, 12, 215–238. reconstruction of Ce-MOF with active sites for efficient
[23] Norris, D. J.; Efros, A. L.; Erwin, S. C. Doped nanocrystals. Science
‫ڀ‬
electrocatalytic N2 reduction. ACS Appl. Energy Mater. 2021, 4,
2008, 319, 1776–1779. 12128–12136.
‫ڀ‬
Nano Res. 2023, 16(5): 6544–6551 6551
‫ڀ‬
[42] Zhang, M.; Zhang, L.; Wang, H.; Bian, Z. Y. Hybrid electrocatalytic
‫ڀ‬
[52] Zhao, Z. Q.; Park, J.; Choi, C.; Hong, S.; Hui, X. C.; Zhang, H.;
‫ڀ‬
ozonation treatment of high-salinity organic wastewater using Ni- Benedict Lo, T. W.; Robertson, A. W.; Lv, Z. X.; Jung, Y. et al.
Ce/OMC particle electrodes. Sci. Total Environ. 2020, 724, 138170. Engineering vacancy and hydrophobicity of two-dimensional TaTe2
[43] Dai, Z.; Qin, F.; Zhao, H. P.; Ding, J.; Liu, Y. L.; Chen, R. Crystal
‫ڀ‬
for efficient and stable electrocatalytic N2 reduction. Innovation
defect engineering of aurivillius Bi2MoO6 by Ce doping for 2022, 3, 100190.
increased reactive species production in photocatalysis. ACS Catal. [53] Liu, Q.; Li, X. L.; He, Q.; Khalil, A.; Liu, D. B.; Xiang, T.; Wu, X.
‫ڀ‬
J.; Song, L. Gram-scale aqueous synthesis of stable few-layered 1T-

2016, 6, 3180–3192.
MoS2: Applications for visible-light-driven photocatalytic hydrogen
[44] Liu, P.; Li, J. W.; Yan, J. Y.; Song, W. B. Defect-rich Fe-doped
evolution. Small 2015, 11, 5556–5564.
‫ڀ‬
NiS/MoS2 heterostructured ultrathin nanosheets for efficient overall

[54] Wang, D. Z.; Zhang, X. Y.; Bao, S. Y.; Zhang, Z. T.; Fei, H.; Wu, Z.
water splitting. Phys. Chem. Chem. Phys. 2022, 24, 8344–8350.
‫ڀ‬
Z. Phase engineering of a multiphasic 1T/2H MoS2 catalyst for

[45] Tao, L.; Duan, X. D.; Wang, C.; Duan, X. F.; Wang, S. Y. Plasma-
highly efficient hydrogen evolution. J. Mater. Chem. A 2017, 5,
‫ڀ‬
engineered MoS2 thin-film as an efficient electrocatalyst for

2681–2688.
hydrogen evolution reaction. Chem. Commun. 2015, 51, 7470–7473.
[55] Wang, J. Y.; Tang, J.; Guo, T.; Zhang, S. H.; Xia, W.; Tan, H. B.;
[46] Huang, W. T.; Zhou, Q. W.; Su, S. Q.; Li, J.; Lu, X. B.; Gao, X. S.;
‫ڀ‬
Bando, Y.; Wang, X.; Yamauchi, Y. C3N4-digested 3D construction

‫ڀ‬
Wang, X.; Jin, M. L.; Zhou, G. F.; Zhang, Z. et al. Ion beam defect
of hierarchical metallic phase MoS2 nanostructures. J. Mater. Chem.
engineering on ReS2/Si photocathode with significantly enhanced
A 2019, 7, 18388–18396.
hydrogen evolution reaction. Adv. Mater. Interfaces 2019,
[56] Plecháček, T.; Navrátil, J.; Horák, J.; Lošt’ák, P. Defect structure of
6, 1801663.
‫ڀ‬
Pb-doped Bi2Te3 single crystals. Philos. Mag. 2004, 84, 2217–2228.

[47] Sun, Y. J.; Liang, Y. X.; Luo, M. C.; Lv, F.; Qin, Y. N.; Wang, L.;
‫ڀ‬
[57] Kim, Y. H.; Kim, Y.; Kim, H. S.; Choi, S. M.; Kim, S. I.; Lee, K. H.
Xu, C.; Fu, E. G.; Guo, S. J. Defects and interfaces on PtPb
‫ڀ‬
Concentration-dependent excess Cu doping behavior and influence

nanoplates boost fuel cell electrocatalysis. Small 2018, 14, 1702259. on thermoelectric properties in Bi2Te3. Int. J. Energy Res. 2022, 46,
[48] Geng, Z.; Liu, Y.; Kong, X.; Li, P.; Li, K.; Liu, Z.; Du, J.; Shu,
‫ڀ‬
3707–3713.
M.; Si, R.; Zeng, J. Achieving a record-high yield rate of [58] Zhao, Y. M.; Rabouw, F. T.; van Puffelen, T.; van Walree, C. A.;
‫ڀ‬
120.9 μgNHŶ·mgcat.−1·h−1 for N2 electrochemical reduction over Ru Gamelin, D. R.; de Mello Donegá, C.; Meijerink, A. Lanthanide-
single-atom catalysts. Adv. Mater. 2018, 30, 1803498. doped CaS and SrS luminescent nanocrystals: A single-source
[49] Wang, J.; Huang, B. L.; Ji, Y. J.; Sun, M. Z.; Wu, T.; Yin, R. G.;
‫ڀ‬
precursor approach for doping. J. Am. Chem. Soc. 2014, 136,

Zhu, X.; Li, Y. Y.; Shao, Q.; Huang, X. Q. A general strategy to 16533–16543.
glassy M-Te (M = Ru, Rh, Ir) porous nanorods for efficient [59] Kiriya, D.; Tosun, M.; Zhao, P. D.; Kang, J. S.; Javey, A. Air-stable
‫ڀ‬
electrochemical N2 fixation. Adv. Mater. 2020, 32, 1907112. surface charge transfer doping of MoS2 by benzyl viologen. J. Am.
[50] Chen, C.; Zhu, X. R.; Wen, X. J.; Zhou, Y. Y.; Zhou, L.; Li, H.; Tao,
‫ڀ‬
Chem. Soc. 2014, 136, 7853–7856.

L.; Li, Q. L.; Du, S. Q.; Liu, T. T. et al. Coupling N2 and CO2 in H2O [60] Bi, J. H.; Ying, H.; Xu, H.; Zhao, X. Y.; Du, X. Y.; Hao, J. C.; Li, Z.
‫ڀ‬
to synthesize urea under ambient conditions. Nat. Chem. 2020, 12, H. Phosphorus vacancy-engineered Ce-doped CoP nanosheets for
717–724. the electrocatalytic oxidation of 5-hydroxymethylfurfural. Chem.
[51] Liu, Y. Q.; Huang, L.; Fang, Y. X.; Zhu, X. Y.; Nan, J. L.; Dong, S.
‫ڀ‬
Commun. 2022, 58, 7817–7820.

J. Interfacial electron regulation of Rh atomic layer-decorated SnO2 [61] Yan, G. Y.; Wu, T.; Xing, S. M.; Chen, F.; Zhao, B. W.; Gao, W. J.
‫ڀ‬
heterostructures for enhancing electrocatalytic nitrogen reduction. Ultrathin Ce-doped La2O3 nanofilm electrocatalysts for efficient
ACS Appl. Mater. Interfaces 2022, 14, 12304–12313. oxygen evolution reactions. Nanotechnology 2022, 33, 245405.
‫ڀ‬

$sztubm Efgfdu Fohjoffsjoh PG #J 5F Oboptiffut CZ $F Epqjoh Gps Fggjdjfoufmfduspdbubmzujdojusphfosfevdujpo

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

$sztubm Efgfdu Fohjoffsjoh PG #J 5F Oboptiffut CZ $F Epqjoh Gps Fggjdjfoufmfduspdbubmzujdojusphfosfevdujpo

Uploaded by

Copyright:

Available Formats

Research Article

ISSN 1998-0124 CN 11-5974/O4

OBOPTIFFUT DPOUBJOJOH B MBSHF OVNCFS PG UFMMVSJVN WBDBODJFT CZ

www.theNanoResearch.com | www.Springer.com/journal/12274 | Nano Research

www.theNanoResearch.com | www.Springer.com/journal/12274 | Nano Research

Chemical shift (ppm)

EJGGFSFOUQPUFOUJBMTJO/TBUVSBUFE./B40TPMVUJPO D 67oWJTTQFDUSBPGUIFFMFDUSPMZUFBGUFSFMFDUSPMZTJTBUUIFDPSSFTQPOEJOHQPUFOUJBMTGPSI E /)ZJFME

UIF&4. SFTVMUJOHGSPNUIFTIBSQMZQSPNPUFEDPNQFUJUJWF)&3 TVCTUSBUFBOEUIFEPQJOHFMFNFOUJTUIFDPSFPGUIFEPQJOHTUSBUFHZ

GVSUIFS EFUBJMT PG UIF FYQFSJNFOUBM TFDUJPO DPSSFTQPOEJOH

SFEVDJOH UIF JNQFEBODF PG UIF NBUFSJBMT $PNQBSFE UP QSJTUJOF

alternative to the Haber–Bosch process. Nat. Catal. 2019, 2,

low temperature. Joule 2018, 2, 846–856.

G. W.; Zhang, F.; Asiri, A. M.; Sun, X. P. An amorphous WC thin

www.theNanoResearch.com | www.Springer.com/journal/12274 | Nano Research

Chem., Int. Ed. 2012, 51, 3147–3151.

Angew. Chem., Int. Ed. 2015, 54, 9266–9270.

layered Bi2Te3 nanoplates/graphene composite with high gravimetric

J.; Yang, S. Y.; Jin, Z. Review on photocatalytic and electrocatalytic

1229–1249. Lee, K. H.; Jeong, U. Synthesis of multishell nanoplates by

S. Y.; Asiri, A. M.; Ma, D. W.; Sun, X. P. Iron-group

269–275. Wang, L.; Wang, H. J. Two-dimensional heterojunction

Ed. 2020, 59, 10888–10893. transport properties of morphology-dependent two-dimensional

J.; Song, L. Gram-scale aqueous synthesis of stable few-layered 1T-

NiS/MoS2 heterostructured ultrathin nanosheets for efficient overall

Z. Phase engineering of a multiphasic 1T/2H MoS2 catalyst for

engineered MoS2 thin-film as an efficient electrocatalyst for

Bando, Y.; Wang, X.; Yamauchi, Y. C3N4-digested 3D construction

Pb-doped Bi2Te3 single crystals. Philos. Mag. 2004, 84, 2217–2228.

Concentration-dependent excess Cu doping behavior and influence

precursor approach for doping. J. Am. Chem. Soc. 2014, 136,

Chem. Soc. 2014, 136, 7853–7856.

Commun. 2022, 58, 7817–7820.

www.theNanoResearch.com | www.Springer.com/journal/12274 | Nano Research

You might also like

EJGGFSFOUQPUFOUJBMTJO/TBUVSBUFE./B40TPMVUJPO D 67oWJTTQFDUSBPGUIFFMFDUSPMZUFBGUFSFMFDUSPMZTJTBUUIFDPSSFTQPOEJOHQPUFOUJBMTGPSI E /)ZJFME

SFEVDJOH UIF JNQFEBODF PG UIF NBUFSJBMT $PNQBSFE UP QSJTUJOF