PMID- 31260279
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20200225
IS  - 1520-5126 (Electronic)
IS  - 0002-7863 (Print)
IS  - 0002-7863 (Linking)
VI  - 141
IP  - 28
DP  - 2019 Jul 17
TI  - Sustained Solar H(2) Evolution from a Thiazolo[5,4-d]thiazole-Bridged Covalent 
      Organic Framework and Nickel-Thiolate Cluster in Water.
PG  - 11082-11092
LID - 10.1021/jacs.9b03243 [doi]
AB  - Solar hydrogen (H(2)) evolution from water utilizing covalent organic frameworks 
      (COFs) as heterogeneous photosensitizers has gathered significant momentum by 
      virtue of the COFs' predictive structural design, long-range ordering, tunable 
      porosity, and excellent light-harvesting ability. However, most photocatalytic 
      systems involve rare and expensive platinum as the co-catalyst for water 
      reduction, which appears to be the bottleneck in the development of economical 
      and environmentally benign solar H(2) production systems. Herein, we report a 
      simple, efficient, and low-cost all-in-one photocatalytic H(2) evolution system 
      composed of a thiazolo[5,4-d]thiazole-linked COF (TpDTz) as the photoabsorber and 
      an earth-abundant, noble-metal-free nickel-thiolate hexameric cluster co-catalyst 
      assembled in situ in water, together with triethanolamine (TEoA) as the 
      sacrificial electron donor. The high crystallinity, porosity, photochemical 
      stability, and light absorption ability of the TpDTz COF enables excellent 
      long-term H(2) production over 70 h with a maximum rate of 941 mumol h(-1) g(-1), 
      turnover number TON(Ni) > 103, and total projected TON(Ni) > 443 until complete 
      catalyst depletion. The high H(2) evolution rate and TON, coupled with long-term 
      photocatalytic operation of this hybrid system in water, surpass those of many 
      previously known organic dyes, carbon nitride, and COF-sensitized photocatalytic 
      H(2)O reduction systems. Furthermore, we gather unique insights into the reaction 
      mechanism, enabled by a specifically designed continuous-flow system for 
      non-invasive, direct H(2) production rate monitoring, providing higher accuracy 
      in quantification compared to the existing batch measurement methods. Overall, 
      the results presented here open the door toward the rational design of robust and 
      efficient earth-abundant COF-molecular co-catalyst hybrid systems for sustainable 
      solar H(2) production in water.
FAU - Biswal, Bishnu P
AU  - Biswal BP
AUID- ORCID: 0000-0002-8565-4550
AD  - Max Planck Institute for Solid State Research , Heisenbergstrasse 1 , 70569 
      Stuttgart , Germany.
FAU - Vignolo-Gonzalez, Hugo A
AU  - Vignolo-Gonzalez HA
AD  - Max Planck Institute for Solid State Research , Heisenbergstrasse 1 , 70569 
      Stuttgart , Germany.
AD  - Department of Chemistry , University of Munich (LMU) , Butenandtstrasse 5-13 , 
      81377 Munchen , Germany.
FAU - Banerjee, Tanmay
AU  - Banerjee T
AUID- ORCID: 0000-0002-4548-2117
AD  - Max Planck Institute for Solid State Research , Heisenbergstrasse 1 , 70569 
      Stuttgart , Germany.
FAU - Grunenberg, Lars
AU  - Grunenberg L
AD  - Max Planck Institute for Solid State Research , Heisenbergstrasse 1 , 70569 
      Stuttgart , Germany.
AD  - Department of Chemistry , University of Munich (LMU) , Butenandtstrasse 5-13 , 
      81377 Munchen , Germany.
FAU - Savasci, Gokcen
AU  - Savasci G
AUID- ORCID: 0000-0002-6183-7715
AD  - Max Planck Institute for Solid State Research , Heisenbergstrasse 1 , 70569 
      Stuttgart , Germany.
AD  - Department of Chemistry , University of Munich (LMU) , Butenandtstrasse 5-13 , 
      81377 Munchen , Germany.
FAU - Gottschling, Kerstin
AU  - Gottschling K
AD  - Max Planck Institute for Solid State Research , Heisenbergstrasse 1 , 70569 
      Stuttgart , Germany.
AD  - Department of Chemistry , University of Munich (LMU) , Butenandtstrasse 5-13 , 
      81377 Munchen , Germany.
FAU - Nuss, Jurgen
AU  - Nuss J
AUID- ORCID: 0000-0002-0679-0184
AD  - Max Planck Institute for Solid State Research , Heisenbergstrasse 1 , 70569 
      Stuttgart , Germany.
FAU - Ochsenfeld, Christian
AU  - Ochsenfeld C
AUID- ORCID: 0000-0002-4189-6558
AD  - Department of Chemistry , University of Munich (LMU) , Butenandtstrasse 5-13 , 
      81377 Munchen , Germany.
AD  - Center for Nanoscience , Schellingstrasse 4 , 80799 Munchen , Germany.
FAU - Lotsch, Bettina V
AU  - Lotsch BV
AUID- ORCID: 0000-0002-3094-303X
AD  - Max Planck Institute for Solid State Research , Heisenbergstrasse 1 , 70569 
      Stuttgart , Germany.
AD  - Department of Chemistry , University of Munich (LMU) , Butenandtstrasse 5-13 , 
      81377 Munchen , Germany.
AD  - Center for Nanoscience , Schellingstrasse 4 , 80799 Munchen , Germany.
AD  - Nanosystems Initiative Munich (NIM) , Schellingstrasse 4 , 80799 Munchen , 
      Germany.
LA  - eng
PT  - Journal Article
DEP - 20190701
PL  - United States
TA  - J Am Chem Soc
JT  - Journal of the American Chemical Society
JID - 7503056
SB  - IM
PMC - PMC6646957
COIS- The authors declare no competing financial interest.
EDAT- 2019/07/02 06:00
MHDA- 2019/07/02 06:01
PMCR- 2019/07/23
CRDT- 2019/07/02 06:00
PHST- 2019/07/02 06:00 [pubmed]
PHST- 2019/07/02 06:01 [medline]
PHST- 2019/07/02 06:00 [entrez]
PHST- 2019/07/23 00:00 [pmc-release]
AID - 10.1021/jacs.9b03243 [doi]
PST - ppublish
SO  - J Am Chem Soc. 2019 Jul 17;141(28):11082-11092. doi: 10.1021/jacs.9b03243. Epub 
      2019 Jul 1.