Pho oca aly ic T ans e Hyd ogena ion Reac ions Using Wa e as
he P o on Sou ce
En Zhao, Wenjun Zhang, Lin Dong, Radek Zbo il,*and Zupeng Chen*
Ci e This: ACS Ca al. 2023, 13, 7557−7567
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ABSTRACT: T ans e hyd ogena ion using liquid hyd ogen ca ie s as
he di ec p o on sou ces unde mild condi ions has ecei ed ex ensi e
a en ion in he esea ch a ea o o ganic syn hesis. The eme ging
pho oca aly ic wa e -dona ing ans e hyd ogena ion (PWDTH) is a
p omising al e na i e o e he con en ional hyd ogena ion echnology
due o he ad an ages o being eco- iendly. This pape ocuses on he
ecen ad ances in he ising and apidly de eloping ield o PWDTH
eac ions, de o ed o elucida ing he mechanism o he hyd ogen ans e
p ocess and a ionalizing he design p inciples o e icien pho oca alys s.
Finally, he cu en challenges and u u e oppo uni ies a e desc ibed.
KEYWORDS: pho oca alysis, ans e hyd ogena ion, wa e spli ing, mild condi ions, deu e a ion
1. INTRODUCTION
Hyd ogena ion, as one o he mos impo an pilla s o he
chemical indus y, has been widely used in he pe ochemical,
coal chemical, ine chemical, and pha maceu ical indus ies,
and i has been assessed ha 25% o chemical ans o ma ions
in ol e a leas one hyd ogena ion s ep.
1,2
T adi ional he mal
hyd ogena ion is an ene gy-in ensi e p ocess ha usually
equi es ha sh condi ions o high empe a u e and p essu e
wi h a lammable H2a mosphe e (Scheme 1).
3,4
The ans e
hyd ogena ion (TH) eac ion, e e ing o he addi ion o
hyd ogen o an o ganic molecule om a non-H2sou ce (e.g.,
o mic acid, silane, and bo ane−ammonia), is a p ospec i e
me hod o access a ious hyd ogena ed o ganics.
3
Fo
ins ance, Xu e al. epo ed he TH o alkene by aking
ammonia bo ane as a hyd ogen sou ce.
5
Kappe e al. p esen ed
a ca alys - ee p ocess o he in si u gene a ion o diimide,
which was applied o he educ ion o alkenes.
6
Zbo il e al.
epo ed he selec i e hyd ogena ion o ni oa oma ics using
hyd azine as a p o on sou ce.
7
Mo eo e , alcohols and acids
a e also used as p o on sou ces o he hyd ogena ion o
di e se unsa u a ed bonds.
8−13
Ne e heless, hese sys ems
ha e he disad an age o he use o non-en i onmen ally
iendly p o on sou ces (Scheme 1).
In conside a ion o he ul ima e goal o de eloping eco-
iendly and sus ainable p ocesses in chemical indus y
p oduc ion, wa e is ega ded as he ul ima e g een sou ce o
a hyd ogen dono o TH.
14
Un o una ely, he ac i a ion o
wa e molecules is ex emely challenging unde mild
condi ions due o i s in insic he mos abili y (ΔG°= +237
Recei ed: Janua y 21, 2023
Re ised: Ap il 1, 2023
Published: May 21, 2023
Scheme 1. T adi ional The mal Hyd ogena ion Uses
Flammable H2a High Tempe a u e and P essu e and
Con en ional TH Uses Eco-Un iendly Hyd ogen Sou ces
(e.g., Fo mic Acid, Hyd azine, and Bo ane−Ammonia),
while Pho oca aly ic T ans e Hyd ogena ion Uses H2O as
he G een Hyd ogen Sou ce a No mal P essu e and
Tempe a u e
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kJ mol−1).
15,16
T emendous e o s had been de o ed o
explo ing he easibili y o wa e as a hyd ogen sou ce. Fo
example, S okes e al. showed ha he haza dous addi i e
B2(OH)4could media e he ans e o H o D a oms om
H2O o deu e a ed D2O o alkenes and alkynes.
17
The
explosi e magnesium
18
and manganese
19
powde s we e also
employed o ac i a e H−O bonds in wa e o he hyd o-
gena ion o unsa u a ed bonds. These echnologies ha e
p o ided new oppo uni ies in H−O bond ac i a ions, bu
hey ha e impo an limi a ions due o he use o haza dous o
oxic species. This encou ages he employmen o a sa e and
sus ainable me hod o ac i a e he wa e molecules.
The de elopmen o pho oca aly ic wa e spli ing has
inspi ed sus ainable concep s o he gene a ion o “g een
hyd ogen” wi hin chemical ene gy s o age schemes, enabling
he pu sui o ca bon neu ali y and alle ia ing he ene gy c isis
associa ed wi h he deple ion o ossil uels. I is well-known
ha H2is one o he mos a ac i e uels because i possesses a
high ene gy densi y and does no p oduce pollu an s du ing
combus ion.
20
Howe e , he e icien s o age and anspo o
lammable H2is challenging and inc eases he cos s o he
hyd ogena ion indus y. In his con ex , he u iliza ion o he
ac i e hyd ogen in e media es (H*) de i ed om wa e
spli ing o he hyd ogena ion o unsa u a ed bonds is
in iguing (Scheme 1). The e o e, he pho oca aly ic wa e -
dona ing ans e hyd ogena ion (PWDTH) e icien ly in e-
g a es he p ocesses o pho oca aly ic wa e spli ing and
hyd ogena ion, which could ac i a e wa e unde mild
condi ions, a e he s o age and anspo o H2, and gene a e
high- alue-added o ganic p oduc s in a mo e sus ainable
manne .
14−16
Mul iple excellen e iews ha e p o ided comp ehensi e
co e age o ans e hyd ogena ion eac ions in he moca a-
ly ic, elec oca aly ic, and pho oca aly ic p ocesses, including
he explo a ion o ansi ion-me al ca alys di e si y, he use o
g een hyd ogen dono s, and he in es iga ion o TH
mechanisms.
2−4,21−23
Fo ins ance, Choudhu y’s g oup
e iewed he ad an ages o using biomass-de i ed alcohols as
hyd ogen sou ces o eplace non enewable H2gas o he TH
o CO2.
21
Xu’s g oup ou lined ca aly ic TH using o mic acid
o o ma e as an al e na i e o high-p essu e hyd ogen, despi e
he ine i able decomposi ion o FA o o ma e o he
g eenhouse gas CO2du ing he ca aly ic p ocess.
22
Un o u-
na ely, he e is s ill no sys ema ic summa y concen a ing on
he pho oca aly ic ans e hyd ogena ion using wa e as he
ul ima e g een p o on sou ce unde mild condi ions. He ein,
we p esen a imely and concise pe spec i e o he ecen
p og ess o he pho oca aly ic wa e -dona ing ans e hyd o-
gena ion eac ions (Scheme 1). We i s e eal he mechanism
o PWDTH in his pe spec i e. Then, he a ional design o
pho oca alys s (i.e., single-a om ca alys s and alloy ca alys s) o
achie e e icien con e sion and high selec i i y o PWDTH is
emphasized. Fu he mo e, pho oca aly ic deu e a ion using
D2O as a deu e ium sou ce is discussed. Finally, he challenges
and oppo uni ies a e add essed o p o ide in iguing
pe spec i es o u he ad ance he PWDTH eac ions.
2. FUNDAMENTALS OF PHOTOCATALYTIC
WATER-DONATING TRANSFER HYDROGENATION
Pho oca aly ic wa e spli ing in o H2is widely ega ded as a
p ominen app oach o s o ing sola ene gy as chemical
ene gy.
24
Meanwhile, pho oca alysis has e ol ed o e he las
decades in o a b oadly used app oach o o ganic syn hesis
(e.g., ans e hyd ogena ion).
25
Inspi ed by hese s udies, a
seminal wo k in he ield o PWDTH was epo ed by Knech ’s
g oup in 2014.
26
They de eloped a palladium nanopa icle
deco a ed Cu2O ca alys (Cu2O/Pd) ia a gal anic exchange,
which used he in si u gene a ed H2 om pho oca aly ic wa e
spli ing a he Cu2O su ace o he subsequen hyd o-
dehalogena ion o polychlo ina ed biphenyls a he Pd
nanopa icles (Figu e 1a). Figu e 1b shows ha 3-chlo obi-
phenyl (PCB2) could be ully dechlo ina ed o biphenyl wi hin
15 h unde isible-ligh i adia ion. Howe e , he wo k did no
ack he pa hway o hyd ogen addi ion du ing he PWDTH
eac ion, which is undamen al o he mechanis ic s udy.
Likewise, al hough he g oups o Qiu
27
and Su
28
epo ed he
PWDTH eac ion using he in si u gene a ed H*species om
wa e , he p esence o addi i es (i.e., HCOOH and NaHSO4)
inc eases he di icul y o mechanism in es iga ion (Scheme
2a,b). Mo eo e , Su e al. p esen ed he deu e a ion o alkenes
and alkynes u ilizing he in si u gene a ed deu e ium species
(D*) om D2O spli ing.
29
Un o una ely, he p esence o
CD3OD in he eac ion sys em complica ed he iden i ica ion
o he sou ce o ac i e D species (Scheme 2c).
2.1. Mechanism In es iga ion. To disclose he o igin o
he hyd ogen addi ion in he PWDTH eac ion, Xu e al.
employed iso ope-labeling expe imen s,
15
in which s y ene was
es ed as a model compound owa d TH. As shown in he mass
spec a (Figu e 2, op), when H2O was used, he m/z alues o
91.1 and 106.1 we e assigned o he agmen a ion ion [ph-
Figu e 1. (a) Illus a ion o ab ica ion o Cu2O/Pd ca alys s o
pho oca aly ic wa e -dona ing dehalogena ion. (b) Concen a ion
changes o PCB2 and biphenyl p oduc du ing he pho oca aly ic
wa e -dona ing dehalogena ion eac ion o e Cu2O/Pd. Reac ion
condi ions: ca alys (100 mg), subs a e (1.25 μmol), H2O (25 mL),
CH3OH (25 mL), 450 W Hg lamp, p essu e (1 ba ), N2a mosphe e.
Rep oduced wi h pe mission om e 26. Copy igh 2014 Ame ican
Chemical Socie y.
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CH2]+and he molecula ion o e hylbenzene, espec i ely.
These signals shi ed o 92.1 and 108.1 when eplacing H2O
wi h D2O, sugges ing ha he p o on sou ce o TH o igina es
om wa e . Howe e , his me hod canno iden i y he pa hway
o hyd ogen addi ion in ac ual scena ios. To add ess he
ma e , ou ecen s udy employed ope ando nuclea magne ic
esonance (NMR) measu emen s o he i s ime o ack he
eac ion pa hway du ing he PWDTH eac ion.
14
As shown in
he 1H NMR spec a (Figu e 2, bo om), p o on signals om
he benzene ing ( egion a) and e henyl ( egions b−d) o he
s y ene molecule we e obse ed unde da k condi ions. Then,
he signals o s y ene emained un ouched a e 2 h in he da k,
sugges ing ha he s y ene is s eady unde da k condi ions and
he unsa u a ed s uc u e eluc an ly exchanges p o ons wi h
D2O. A e in si u illumina ion o 2 h, he e henyl signal
diminished, and he me hyl s uc u e ( egion e) on e hyl-
benzene began o appea , e i ying he con e sion o s y ene
owa d e hylbenzene. No ably, a g ea deal o D2O was
ac i a ed unde he i adia ion condi ions and he D o D2O
unde wen a apid p o on exchange wi h he H o he benzene
s uc u e, b oadening he 1H NMR signals o he benzene ing
in he egion a. To exclude he possibili y o indi ec
hyd ogena ion o s y ene wi h he gene a ed H2 om wa e
spli ing, 1 ba o hyd ogen gas was ed in o he ope ando
closed NMR ube. The esul s indica e ha he p o on
addi ion occu s in bo h he benzene ing and e henyl, whe eas
he p o on addi ion only occu s in he e henyl s uc u e
wi hou H2in oduc ion. The e o e, he ope ando NMR
expe imen s unequi ocally p o e ha he p o on addi ion
mechanism om s y ene o e hylbenzene is a di ec hyd o-
gena ion eac ion u ilizing he in si u gene a ed p o ons om
pho oca aly ic wa e spli ing ins ead o in si u gene a ed H2
gas. Mo eo e , he s ong p o on exchange could e icien ly
ac i a e wa e molecules o pho oca aly ic ans e hyd o-
gena ion.
T adi ional he mal hyd ogena ion wi h lammable H2is
ca ied ou o e ansi ion-me al ca alys s, which consis s o
mul iple s eps including bond clea age, ea angemen , and
ecombina ion.
22
In e ms o he PWDTH eac ion, H2is
eplaced by H* om pho oca aly ic wa e spli ing, whe e he
H*could be used in he subsequen hyd ogena ion s ep and
spill o e om he me al si es o e ol e in o H2. Due o he
compe i ion be ween hese wo eac ions, explo ing he sub le
ela ionship be ween hyd ogena ion and hyd ogen e olu ion
p o ides insigh in o he mechanism o he PWDTH eac ion.
Scheme 2. Illus a ion o he PWDTH P ocess in he
P esence o Hyd ogen-Rich Addi i es
a
a
Reac ion condi ions: (a) ca alys (10 mg), subs a e (0.1 mmol),
H2O (1.5 mL), e hyl ace a e (2 mL), CH3OH (1.4 mL), addi i e
(HCOOH, 0.1 mL), 20 W blue ligh (λ= 420 nm), empe a u e (298
K), p essu e (1 ba ), A a mosphe e; (b) ca alys (10 mg), subs a e
(0.1 mmol), H2O (1.5 mL), e hyl ace a e (2 mL), CH3OH (1.5 mL),
addi i e (NaHSO4, 0.1 mmol), 20 W blue ligh (λ= 420 nm),
empe a u e (298 K), p essu e (1 ba ), A a mosphe e; (c) ca alys
(10 mg), subs a e (0.1 mmol), D2O (1.5 mL), e hyl ace a e (2 mL),
CD3OD (1.5 mL), addi i e (AlCl3, 0.1 mmol), 20 W blue ligh (λ=
420 nm), empe a u e (298 K), p essu e (1 ba ), A a mosphe e.
Figu e 2. ( op) Mass spec a o he liquid p oduc om he PWDTH
eac ion o s y ene. Rep oduced wi h pe mission om e 15.
Copy igh 2020 Ame ican Chemical Socie y. (bo om) Ope ando
1H NMR spec a o he liquid p oduc om he PWDTH eac ion o
s y ene. Rep oduced wi h pe mission om e 14. Copy igh 2022
Wiley.
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Fo example, Xiong and co-wo ke s used a TiO2−Pd0.5P 0.5
hyb id ca alys o he PWDTH eac ion and hey de ec ed he
amoun o hyd ogen e olu ion in he p esence and absence o
he subs a e, espec i ely.
30
Compa ed o a la ge amoun o
hyd ogen e olu ion in he absence o a subs a e, he ca alys
exhibi ed li le hyd ogen e olu ion ac i i y in he p esence o a
subs a e, indica ing ha mos o H*(ca. 99% H*) was
ans e ed o he hyd ogena ion eac ion. This is due o he
adso p ion o H*on he Pd su ace as a hollow-si e
con igu a ion wi h s ong binding (discussed in de ail in
subsequen subsec ions). Simila phenomena ha e been ound
in o he PWDTH sys ems, whe e ei he nanopa icle
ca alys s
15,31
o he e ojunc ions
32
we e used. In ou p e ious
wo k,
14
we de eloped a palladium single-a om ca alys o he
PWDTH eac ion, and he pe o mance o he ans e
hyd ogena ion was much imp o ed compa ed o he abo e
wo ks due o he in insic p ope ies o he single-a om
ca alys , esul ing in supe io hyd ogen e olu ion ac i i y and
an abundance o ca aly ically ac i e si es. Howe e , he
p opo ion o he H*used in he PWDTH eac ion has
declined (ca. 85% H*) compa ed o he abo e wo ks,
sugges ing ha single-a om ca alys s ine i ably was e some o
he H*while imp o ing he PWDTH pe o mance. In
summa y, e y ew wo ks ha e been done o in es iga e he
compe i ion be ween hyd ogena ion and H2e olu ion.
A ailable s udies ha e ound ha mos o he H*is
p e e en ially used in PWDTH eac ions, and his is mo e
e iden in nanopa icle o he e ojunc ion ca alys s (i.e.,
ca alys s wi h lowe wa e -spli ing ac i i y). Al hough single-
a om ca alys s could enhance he pe o mance o PWDTH
eac ions, hey also p omo e hyd ogen e olu ion. The e ec o
he s uc u e o pho oca alys s on he compe i ion be ween
hyd ogena ion and H2e olu ion emains unknown. As mo e
esea ch is conduc ed, he ela ionship be ween hem may be
clea e .
Resea che s ha e employed a ious echniques o p obe he
eac ion mechanism o he subsequen hyd ogena ion p ocess.
To explo e he de ailed p ocesses o he hyd ogena ion o
ni obenzene o aniline, Xu e al. employed in si u di use
e lec ance in a ed Fou ie ans o m spec oscopy
(DRIFTS).
32
Fi s , ni obenzene (PhNO2) adso bed on o
he ca aly ic si e and o med a PhN(OH)2in e media e by wo
H* ans e s, ollowed by he emo al o one molecule o wa e
o o m a PhNO in e media e, hen by wo H* ans e s o
o m a PhNHOH in e media e, ollowed by he emo al o one
molecule o wa e o o m a PhN in e media e, and inally by
wo H* ans e o o m aniline (PhNH2), which was deso bed
om he ca alys . Zhao and co-wo ke s examined a nickel
single-a om ca alys p eadso bed by wa e unde isible-ligh
i adia ion h ough ex ended X- ay abso p ion ine s uc u e
spec a (EXAFS) combined wi h densi y unc ional heo y
(DFT) calcula ions o p opose an adso p ion con igu a ion o
H*(i.e., OH−Ni−N2···N−H).
33
The subsequen semi-
hyd ogena ion o alkynes hen began wi h he ans e o H*
om py idinic N o he adso bed subs a e.
To in es iga e he mechanism o hyd ogena ion o a yl
b omides, Ren e al. conduc ed some con olled expe imen s,
in which he adical inhibi o s 2,6-di- e -bu yl-4-me hylphenol
(BHT) and 2,2,6,6- e ame hyl-1-pipe idinyloxy (TEMPO)
we e added o he eac ion sys em.
34
The esul s showed
ha he p esence o BHT o TEMPO esul ed in a d ama ic
dec ease in he con en o he p oduc a yl compounds. The
elec on-de icien a yl b omides possessed a highe eac i i y
unde he eac ion sys em. A single elec on ans e (SET)
mechanism could heo e ically explain such an elec on e ec ,
as an inc ease in he elec on densi y o he a oma ic ing could
has en he SET om he ca alys o he subs a e by enhancing
he elec on-accep ing capaci y o he subs a e.
35
Fan and co-
wo ke s employed luo escence emission spec oscopy o
moni o he PWDTH p ocess o N-sul onylimines and
simila ly p oposed a SET mechanism (Scheme 3a).
36
Unde
isible ligh i adia ion, he pho oca alys ac-I (ppy)3is exci ed
o p oduce I 3+*, ollowed by a single elec on ans e p ocess
wi h adical A. The esul ing I 2+ is highly educ i e
37
and
he e o e capable o p oducing deu e ium adicals.
38
The
deu e ium adicals a e hen added o he N-sul onylimine,
which p oduces he inal p oduc s by u he quenching o
adical D. Llo e -Fillol e al. p oposed ha he hyd ogena ion
o a oma ic ke ones could p oceed ia a single elec on
ans e −hyd ogen a om ans e (SET-HAT) mechanism
(Scheme 3b), which was con i med by adical clock expe i-
men s.
39
I is well-known ha [Cu(ba hocup oine)-
(Xan phos)](PF6) (PSCu), a pho o edox ca alys , is exci ed
unde ligh i adia ion and hen educ i ely quenched by an
elec on dono (ED) o gi e PSCu
−,
40
which educes he
educ ion ca alys [Co(OT )(Py2Ts acn)](OT ) ([Co]) o he
Scheme 3. P oposed Mechanism o he PWDTH P ocess o (a) N-Sul onylimines and (b) A oma ic Ke ones and Aldehydes
a
a
Rep oduced wi h pe mission om e s 36 and 39. Copy igh 2019 Royal Socie y o Chemis y.
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in e media e [CoI].
41
[CoI] is p o ona ed by wa e o o m he
pu a i e [CoIII−H], which is eadily educed o gi e he ac i e
[CoII−H] species. Subsequen ly, o he hyd ogena ion o
ke ones and aldehydes, he subs a e is con e ed o a ca bonyl
adical anion in e media e h ough a single elec on ans e o
PSCu
−. Ul ima ely, he in e media e is con e ed o he p oduc
ia a hyd ogen a om ans e om he [CoII−H] species
(homoly ic pa hway, Scheme 3b, le ). Al e na i ely, a di ec
nucleophilic a ack o a pu a i e [CoII−H] species may be also
conside ed (he e oly ic pa hway, Scheme 3b, igh ). By simila
me hods, hei g oup has p oposed ha he educ ion o
a oma ic ole ins in hei eac ion sys em akes place by a HAT
mechanism, mos likely ia [Co−H] in e media es.
42
2.2. F om Nanopa icle o Single-A om Ca alys s.
Du ing he PWDTH eac ion, he pho ogene a ed H* om
wa e spli ing could be adso bed o he su ace o me al
species and subsequen ly added o a ious unsa u a ed o ganic
subs a es. Han e al. demons a ed ha ni obenzenes wi h
di e en g oups could be hyd ogena ed o he co esponding
anilines by he H* om pho oca aly ic wa e spli ing o e a
TiO2-suppo ed Pd nanopa icle ca alys (Pd/TiO2).
43
Sim-
ila ly, Xu e al. ealized he p o on addi ion o di e en
unsa u a ed bonds (C�C, C�O, and N�O) o e pla inum
nanopa icle loaded ca bon ni ide (P /CN o P Pd/CN).
15
Un o una ely, hese nanopa icle ca alys s usually su e om
sluggish con e sion e iciency and poo me al u iliza ion
because he me al a oms inside he bulk o nanopa icles a e
inaccessible o he eac an s.
Single-a om ca alys s (SACs) ha e ecen ly ecei ed
ex ensi e esea ch a en ion due o hei maximum me al
dispe sion and a om-u iliza ion e iciency, which ha e exhibi ed
excellen ca aly ic pe o mance in a b oad ange o applica ions
including Suzuki coupling, selec i e oxida ion, hyd o o myla-
ion, e c.
44,45
In ou ecen wo k, we ex ended he employmen
o SACs o pho oca aly ic ans e hyd ogena ion o he i s
ime. The epo ed ca bon ni ide suppo ed palladium SAC
(Pd1-mpg-C3N4) (Figu e 3a,b) showed p eeminen pe o m-
ance in he PWDTH eac ion compa ed o i s nanopa icle
coun e pa wi h a simila Pd loading (PdNP-mpg-C3N4).
14
As
shown in Figu e 3c, a compa ison on a me al basis mani es ed
he highes e hylbenzene o ma ion a e (22.73 mole hylbenzene
molPd
−1h−1) o he 0.54 w % SAC sample. Howe e , he a e
o e hylbenzene o ma ion dec eased linea ly o 2.02
mole hylbenzene molPd
−1h−1when he Pd con en was u he
inc eased o 2.76 w %, which is 11- old lowe han ha o he
op imized Pd1-mpg-C3N4. The inhibi ed eac ion a e could be
a ibu ed o he o ma ion o clus e s o nanopa icles in
samples wi h a Pd loading highe han 0.8 w %, which
emphasizes he ad an ages o he speci ic elec onic p ope ies
(ca ionic o m) o a omically dispe sed si es o e con en ional
ze o alen nanome als owa d he PWDTH eac ion.
The PWDTH eac ions a e a complex class o mul is age
ca aly ic eac ions. In he p ocess, he wa e molecule is i s
spli o p oduce he H*, which is hen ans e ed o
hyd ogena ed ac i e si es whe e he subs a e is adso bed,
and inally, he o ganic unsa u a ed bond is added. In he i s
s ep (i.e., pho oca aly ic wa e spli ing), he a e o he H*
p oduc ion de e mines he a e o he subsequen hyd o-
gena ion s ep. In o he wo ds, he O−H bond dissocia ion o
wa e molecules may be in ol ed in he a e-limi ing s ep.
33
O e he pas decades, esea che s ha e been dedica ed o
boos ing he ac i i y o pho oca aly ic wa e spli ing.
46
Loading o a coca alys has a ac ed a g ea deal o a en ion
due o i s signi ican ad an ages in e ms o enhanced ligh
abso p ion, pho ogene a ed cha ge mig a ion, and su ace
ca aly ic eac ions (e.g., hyd ogena ion, oxida ion, and
coupling).
47,48
The pho oca aly ic wa e spli ing ac i i y o
non-noble-me al-loaded ca alys s, howe e , is cu en ly a
om being on pa wi h noble-me al-loaded ca alys s. As a
esul , he majo i y o s udies on he PWDTH ha e elied on
noble-me al-loaded ca alys s (e.g., PdNP-CN, P NP-CN, PdNP/
TiO2, and Cu2O/PdNP).
15,26,34,43,49
SACs ha e he po en ial o
g ea ly con ibu e o he a ional design o a ge ed ca alys s o
p e e ed ca aly ic pe o mance by ac ing as he pe ec
pla o ms o in es iga e ca aly ic mechanisms a he molecula
o a omic le el and o comp ehend he ela ionship be ween
s uc u e and ca aly ic pe o mance,
50−52
as con i med in ou
p e ious wo k.
14
Meanwhile, non-noble-me al ca alys s should
be in elligen ly cons uc ed o achie e e icien PWDTH in
o de o educe excessi e dependence on noble-me al ca alys s.
Zhao’s g oup designed a Ni2+−N4si e buil on ca bon ni ide
o pho oca alyzed semihyd ogena ion o alkynes using wa e
Figu e 3. (a) Abe a ion-co ec ed high-angle annula da k- ield
scanning ansmission elec on mic oscopic (AC-HAADF-STEM)
image and (b) Fou ie ans o m o Pd K-edge ex ended X- ay
abso p ion ine s uc u e spec a (EXAFS) spec a o Pd1-mpg-C3N4.
Pd oil and PdO we e applied o compa ison pu poses. (c) Me al-
speci ic eac ion a e owa d e hylbenzene o ma ion as a unc ion o
palladium con en o he PWDTH eac ion o s y ene. Reac ion
condi ions: ca alys (10 mg), subs a e (0.1 mmol), H2O (2 mL), 1,4-
dioxane (3 mL), ie hanolamine (0.5 mL), 40 W blue ligh (λ= 427
nm), empe a u e (308 K), p essu e (1 ba ), N2a mosphe e.
Rep oduced wi h pe mission om e 14. Copy igh 2022 Wiley.
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as he hyd ogen sou ce wi hou alkane p oduc ion.
33
Mo e-
o e , Xu and co-wo ke s de eloped a TiO2/Ce2S3S-scheme
he e ojunc ion pho oca alys o aniline p oduc ion by ni o-
benzene hyd ogena ion wi h wa e as he p o on sou ce.
32
This
is an inno a i e wo k, ee om noble-me al ca alys s, bu he
scope o he e ojunc ion pho oca alys s o a ious PWDTH
eac ions needs o be explo ed. In gene al, he design o he
pho oca alys s mus mee he equi emen s o excellen wa e -
spli ing ac i i y and he p esence o hyd ogena ion ac i e si es
(no mally me al species, e.g., VIII subg oup me als). In
addi ion, se e al a icles ha e con i med ha he speci ic
elec onic p ope ies (ca ionic o m) o a omically dispe sed
si es a e pe haps mo e sui able o he PWDTH eac ions.
14,33
2.3. Pho oca aly ic Selec i e T ans e Hyd ogena ion.
Selec i e hyd ogena ion is a class o highly impo an o ganic
ans o ma ions o bo h pe ochemical and ine chemical
indus ies.
2
The c i ical aspec o selec i e hyd ogena ion elies
on he ab ica ion o e icien and selec i e ca alys s. Xiong e
al. epo ed a TiO2−PdxP 1−xhyb id ca alys owa d pho o-
ca aly ic selec i e 2-me hyl-3-bu yn-2-ol (MBY) semihyd oge-
na ion o 2-me hyl-3-bu en-2-ol (MBE) using wa e as a
p o on sou ce (Scheme 4a).
30
As shown in Figu e 4a, he
PdxP 1−xalloys as ly su moun he limi a ions in ca aly ic
ac i i y and semihyd ogena ion selec i i y compa ed wi h pu e
Pd and P . To e eal he mechanism, he au ho s s udied he
hyd ogen e olu ion pe o mance, which is he compe ing
eac ion ha consumes he ac i e H*species (Figu e 4b). A
signi ican ly imp o ed pe o mance o pho oca aly ic hyd ogen
e olu ion was obse ed in he absence o MBY in all samples.
When MBY was in oduced, almos all samples we e inac i e
o he H2e olu ion p ocess excep o pu e P , indica ing ha
H*was mos ly used in he semihyd ogena ion o MBY. In
e ms o pu e P , H*species a e weakly bound o P si es in
ei he op-si e o hollow-si e con igu a ions wi h ba ely any
su ace di usion ba ie . The e o e, H*could eadily spill o e
he su ace and subsequen ly e ol e in o H2, limi ing he
con e sion o MBY. In con as , he adso bed H*s ongly
binds o he Pd su ace by a hollow-si e con igu a ion.
Al hough pu e Pd could e ain a high semihyd ogena ion
selec i i y, he slow H*di usion and deso p ion would be a
bo leneck in imp o ing he con e sion o MBY. Ha ing his in
mind, he au ho s en isaged ha alloying Pd wi h P would
o e Pd−P hollow si es o H*adso p ion, in which he M−H
binding could be adjus ed o a sui able ange o app op ia e
di usion and deso p ion o H*. As expec ed, he selec i i y o
he TiO2−Pd0.5P 0.5 sample emained high when he
con e sion app oached 100% (Figu e 4a). This wo k
emphasized he impo ance o la ice enginee ing design on
pho oca aly ic selec i e hyd ogena ion using wa e as a p o on
sou ce.
Selec i e hyd ogena ion o ace ylene o e hylene in he
p esence o an excess amoun o e hylene is an impo an
p ocess o he pe ochemical indus y since a ppm le el o
ace ylene poisons he e hylene polyme iza ion.
53
Weiss e al.
epo ed a PWDTH sys em ha educes ace ylene o e hylene
wi h ≥99% selec i i y unde bo h noncompe i i e (no e hylene
co eeding) and compe i i e (e hylene co eeding) condi ions.
54
Impo an ly, nea ly 100% con e sion was achie ed in he la e
Scheme 4. Illus a ion o Pho oca aly ic Selec i e T ans e
Hyd ogena ion Using H2O as an H Sou ce
a
a
Reac ion condi ions: (a) ca alys (10 mg), subs a e (0.5 mmol),
H2O (7.5 mL), CH3OH (2.5 mL), 300 W Xe lamp (λ< 400 nm),
p essu e (1 ba ), A a mosphe e; (b) ca alys (0.002 μmol), sensi ize
(0.1 μmol [Ru(bpy)3]2+ o 2.5 mg mpg-CN), subs a e (1 a m C2H2,
≥99.5 ol %), aqueous bica bona e bu e (2 mL, pH 8.4), sodium
asco ba e (0.2 mmol), blue ligh (λ= 450 nm), empe a u e (298 K);
(c) ca alys (30 mg), subs a e (1 a m CO2), H2O (0.1 mL), 300 W
Xe lamp.
Figu e 4. (a) The ca aly ic pe o mance o selec i e 2-me hyl-3-
bu yn-2-ol semihyd ogena ion o 2-me hyl-3-bu en-2-ol (MBY) using
wa e as a p o on sou ce wi h a ious TiO2−PdxP 1−xpho oca alys s.
Reac ion condi ions a e as indica ed in Scheme 4a. (b) The amoun
o hyd ogen e olu ion in he p esence o MBY o he absence o
MBY. Rep oduced wi h pe mission om e 30. Copy igh 2017
Wiley.
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case, which is mo e indus ially ele an (Scheme 4b). This
sys em used a molecula ca alys based on [meso- e a(4-
sul ona ophenyl)po phy ina o]cobal (III) (CoTPPS) ope a -
ing unde ambien condi ions and sensi ized by ei he is(2,2′-
bipy idyl)dichlo o u henium(II) hexahyd a e ([Ru(bpy)3]2+)
o mesopo ous g aphi ic ca bon ni ide (mpg-C3N4) unde
isible ligh . Mo eo e , Xiong e al. ealized 99% selec i e CO2
me hana ion in a pu e wa e sys em by in oducing P single
a oms o de ec i e ca bon ni ide (P @De -CN) (Scheme
4c).
55
Despi e he low ca aly ic ac i i y (6.3 μmolCHd
4gca
−1
h−1), he pho o educ ion o CO2in o a high- alue-added
p oduc in pu e wa e has been demons a ed.
2.4. D2O as a Deu e ium Sou ce. Deu e ium labeling is
essen ial in o ganic syn hesis and he pha maceu ical indus y.
Ne e heless, he s a e-o - he-a C−H/C−D exchange using
noble-me al ca alys s o s ong bases/acids has he disad an-
ages o poo unc ional g oup ole ance and in e io
selec i i y. Loh e al. p oposed an inno a i e s a egy o
con ollable deu e a ion o halogena ed compounds by pho o-
ca aly ic D2O spli ing unde mild condi ions using po ous
CdSe nanoshee s as he ca alys (Scheme 5a).
56
A a ie y o
o ganic iodides including a yl, alkyl, and alkynyl iodides could
be deu e a ed wi h sa is ac o y unc ional g oup ole ance
(Scheme 5b). This app oach is also compe en o deu e a e
less educ i ely labile C−B , C−Cl, and e en C−F bonds in
he p esence o ac i a ing g oups on he benzene ing (Scheme
5c−e). Mo eo e , he au ho s ha e de eloped a D-labeled ool
ki con aining deu e a ed a yl halogen, bo ic acid, alkyne,
alkene, e c., which a e aluable D-con aining building blocks
o d ugs o ad anced ma e ials (Scheme 5 ). This wo k
p o ided an a ac i e and p omising s a egy o con ollable
deu e a ion.
Sho ly he ea e , Wu e al. de eloped he deu e a ion o
a oma ic alcohols wi h D2O as a D sou ce (70−99% D
Scheme 5. (a) Illus a ion o Pho oca aly ic Deu e a ion o Halogena ed Compounds using D2O as a D Sou ce, Scope o
pho oca aly ic (b) C−I, (c) C−B , (d) C−Cl, and (e) C−F o C−D T ans o ma ion, and ( ) D-Labeled Toolbox om
Pho oca aly ic C−I o C−D T ans o ma ion o Medical In e media es
a
a
Reac ion condi ions: ca alys (5 mg), subs a e (0.1 mmol), D2O (1.5 mL), CH3CN (2.5 mL), Na2SO3(1 mmol), 150 W Xe lamp, empe a u e
(298 K), p essu e (1 ba ), A a mosphe e. Rep oduced wi h pe mission om e 56. Copy igh 2017 Na u e Publishing G oup.
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inco po a ion) unde isible-ligh i adia ion using CdSe
quan um do s as he pho oca alys (Scheme 6a).
57
Zhao e
al. ealized he syn hesis o deu e ium-labeled alkenes wi h
dis inguished le els o D inco po a ion (99%) o e nickel
nanopa icles suppo ed on ca bon ni ide (Ni/C3N4)
(Scheme 6b).
58
Also, Sun e al. epo ed a me al- ee de ec i e
ul a hin ZnIn2S4nanoshee (D-ZIS) ca alys o pho o-
ca aly ic deu e a ion o ca bonyls u ilizing he in si u gene a ed
D p o ons om D2O spli ing wi h decen deu e a ion
inco po a ion a ios (Scheme 6c).
59
These s a egies p o ided
p omising insigh s in o he sus ainable and eco- iendly o ganic
syn hesis o alue-added deu e a ed chemicals. In addi ion, all
o he abo e deu e a ion s udies ha e also a emp ed
deu e a ion syn hesis o pha maceu ical in e media es (Figu e
5), poin ing o he po en ial o he PWDTH echnique o he
pha maceu ical indus y. Al hough hey all only a emp ed he
eac ion o one pha maceu ical in e media e, he implica ions
o he de elopmen o a g een and sa e pha maceu ical
indus y could be signi ican .
3. CONCLUSION AND OUTLOOK
Al hough pho oca aly ic ans e hyd ogena ion has ound
widesp ead use o e he las decades, using wa e as he di ec
p o on sou ce emains unde de eloped. The inno a i e
pho oca aly ic wa e -dona ing ans e hyd ogena ion enables
he u iliza ion o ac i e H*species om wa e spli ing o
hyd ogena ion unde mild condi ions. This s a egy is
a ac i e due o he sa e, g een, eco- iendly, and sus ainable
eac ion condi ions. This pe spec i e highligh s he eac ion
pa hways and mechanisms, which p o ide insigh s in o he
cons uc ion o ca aly ic sys ems and he design o e icien
pho oca alys s, and discusses ca alys design, leading o
guidance o ailo ing he ca aly ic ac i i y and selec i i y o
di e en he e ogeneous ca alys s. While some p og ess has
been made in he ield o PWDTH, i is in i s in ancy and many
unsol ed p oblems and challenges emain, as ou lined below.
(1) I is c ucial o enhance he pe o mance o he PWDTH
while a oiding he e olu ion o H* om wa e spli ing.
As a as cu en s udies a e conce ned, mos o he H*
is p io i ized o he PWDTH eac ion, which is mo e
p onounced in nanopa icle o he e ojunc ion ca alys s.
Whe eas o SACs, hey migh boos he pe o mance o
he PWDTH eac ion and hyd ogen e olu ion simul a-
neously. Thus, he compe i i e ela ionship be ween
hyd ogena ion and hyd ogen e olu ion has o be
explo ed. Meanwhile, he egula ion o he suppo ed
me al species (i.e., nanopa icles, clus e s, single a oms,
o syne gis ic e ec o di e en species) should be be e
s udied, which migh lead o unexpec ed esul s in he
PWDTH eac ions.
(2) A p esen , noble-me al ca alys s s ill domina e in
PWDTH eac ions. Due o he sca ci y and expense o
noble me als, i is i al o de elop e icien non-noble-
me al ca alys s such as hose o Ni and Co o PWDTH
eac ions.
(3) Selec i e hyd ogena ion eac ions ha e a wide ange o
applica ions in ine chemicals and pha maceu icals as
well as pe ochemicals. Howe e , pho oca aly ic selec i e
hyd ogena ion using wa e as he hyd ogen sou ce
emains o be de eloped: o example, selec i e hyd o-
gena ion o α,β-unsa u a ed ca bonyl compounds. The
a ional design o highly selec i e and e sa ile pho o-
ca alys s by p ecise modula ion o he local coo dina ion
en i onmen would be a p omising di ec ion.
(4) The majo i y o exis ing s udies o PWDTH eac ions
employ addi ional hole sac i icial agen s (e.g., me hanol,
Scheme 6. Illus a ion o Pho oca aly ic Deu e a ion Using
D2O as a D Sou ce
a
a
Reac ion condi ions: (a) ca alys (20 μM), subs a e (0.2 mmol),
D2O (5 mmol), CH3CN (2 mL), ie hylamine (0.4 mmol), blue ligh
(λ= 450 nm), empe a u e (298 K), p essu e (1 ba ), A a mosphe e;
(b) ca alys (3 mg), subs a e (0.03 mmol), D2O (1.2 mL), CH3CN
(4.8 mL), ie hanolamine (0.6 mmol), blue ligh (λ= 420 nm),
empe a u e (298 K), p essu e (1 ba ), A a mosphe e; (c) ca alys (5
mg), subs a e (0.1 mmol), D2O (1.8 mL), CH3CN (0.2 mL),
Na2SO3(2 mmol), whi e LED ligh (λ> 420 nm), empe a u e (298
K), p essu e (1 ba ), A a mosphe e.
Figu e 5. Deu e a ed syn hesis o pha maceu ical in e media es
h ough he PWDTH echnique: (a) me hyl nico ina e-2-d,
56
(b)
isop opyl 2-(4-((4-chlo ophenyl)(hyd oxy)me hyl-d)phenoxy)-2-
me hylp opanoa e,
57
(c) me hyl pen -4-enoa e-4,5,5-d3,
58
and (d)
isop opyl 2-(4-((4-chlo ophenyl)(hyd oxy-d)me hyl-d)phenoxy)-2-
me hylp opanoa e.
59
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ie hanolamine, ie hylamine, and Na2SO3) o p omo e
he gene a ion o p o ons, which p oduce wo hless
subs ances a he oxida ion side.
30
A p omising s a egy
is o subs i u e he hole sac i icial agen s wi h o he
aluable o ganics, which could p oduce alue-added
educ i e and oxida i e p oduc s a he same ime.
(5) In he PWDTH p ocess, he wa e molecule is i s spli
o p oduce he H*, which is hen ans e ed o
ca aly ically ac i e si es o he hyd ogena ion o o ganics
o spills o e o e ol e in o H2. Ne e heless, he speci ic
eac ion pa hways and mechanisms o PWDTH
eac ions emain complex and ambiguous. The unde -
s anding o eac ion mechanisms equi es mo e wo k,
such as moni o ing he eac ion p ocess a he molecula
le el by u ilizing ad anced in si u/ope ando cha ac e -
iza ion echniques and unde s anding he elemen a y
eac ion mechanism h ough heo e ical calcula ions.
(6) As he mos common and nonpollu ing sol en , wa e
also has eno mous po en ial o use in o he ypes o
eac ions. I has been demons a ed ha wa e can
pa icipa e in eac ions as an oxidizing o educing agen ,
such as hyd ogenolysis
60
and couplings.
61,62
This
p o ides di ec ions o he de elopmen o wa e
in ol emen in eac ions.
In conclusion, al hough he ield is s ill in i s nascen s age
and has many challenges, disco e ies will p opel he ield by
sol ing hese issues wi h an inc easing unde s anding o hei
o ganoca aly ic and pho ochemical eac i i y, which will ha e a
signi ican impac on he ene gy ansi ion o a ze o-ca bon
economy.
■AUTHOR INFORMATION
Co esponding Au ho s
Radek Zbo 
il −Regional Cen e o Ad anced Technologies
and Ma e ials, Czech Ad anced Technology and Resea ch
Ins i u e (CATRIN), PalackyUni e si y Olomouc, Olomouc
783 71, Czech Republic; Nano echnology Cen e, CEET,
VSB-Technical Uni e si y o Os a a, Os a a-Po uba 708
00, Czech Republic; o cid.o g/0000-0002-3147-2196;
Email: [email p o ec ed]
Zupeng Chen −Jiangsu Co-Inno a ion Cen e o E icien
P ocessing and U iliza ion o Fo es Resou ces, In e na ional
Inno a ion Cen e o Fo es Chemicals and Ma e ials,
Nanjing Fo es y Uni e si y, Nanjing 210037, People’s
Republic o China; o cid.o g/0000-0002-7351-3240;
Email: [email p o ec ed]
Au ho s
En Zhao −Jiangsu Co-Inno a ion Cen e o E icien
P ocessing and U iliza ion o Fo es Resou ces, In e na ional
Inno a ion Cen e o Fo es Chemicals and Ma e ials,
Nanjing Fo es y Uni e si y, Nanjing 210037, People’s
Republic o China; o cid.o g/0000-0003-3416-2414
Wenjun Zhang −Jiangsu Co-Inno a ion Cen e o E icien
P ocessing and U iliza ion o Fo es Resou ces, In e na ional
Inno a ion Cen e o Fo es Chemicals and Ma e ials,
Nanjing Fo es y Uni e si y, Nanjing 210037, People’s
Republic o China
Lin Dong −Jiangsu Co-Inno a ion Cen e o E icien
P ocessing and U iliza ion o Fo es Resou ces, In e na ional
Inno a ion Cen e o Fo es Chemicals and Ma e ials,
Nanjing Fo es y Uni e si y, Nanjing 210037, People’s
Republic o China
Comple e con ac in o ma ion is a ailable a :
h ps://pubs.acs.o g/10.1021/acsca al.3c00326
Au ho Con ibu ions
E.Z. w o e he d a o he manusc ip . W.Z., L.D., R.Z., and
Z.C. e ised he manusc ip . R.Z. and Z.C. concei ed and
supe ised he whole p ojec .
No es
The au ho s decla e no compe ing inancial in e es .
■ACKNOWLEDGMENTS
This wo k was suppo ed by he Na ional Na u al Science
Founda ion o China (22202105, 22205113, 22002043), he
Na u al Science Founda ion o Jiangsu P o ince
(BK20210608, BK20210626), he Na u al Science Founda ion
o Jiangsu Highe Educa ion Ins i u ions o China
(21KJA150003, 21KJB150027), and he China Pos doc o al
Science Founda ion (2022M711645).
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