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1.
J Am Chem Soc ; 2020 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-32043354

RESUMO

Two-dimensional (2D) covalent organic frameworks (COFs) are promising metal-free materials for photocatalytic water splitting because of their high surface area and predictability to assemble various molecules with tunable electronic properties. Unfortunately, 2D COFs capable of visible-light-driven photocatalytic overall water splitting are rare, partly due to rigorous requirements to their band alignments and coexistence of catalytic sites for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, 12 2D nitrogen-linked COFs are designed based on first-principles calculations and topological assembly of molecular segments with catalytic activities toward either HER or OER, respectively. The electronic band structures calculated with HSE06 method indicate that 2D COFs are semiconductors with a widely tunable bandgap ranging from 1.92 to 3.23 eV. The positions of both conduction and valence band edges of nine 2D COFs match well with the chemical reaction potential of H2/H+ and O2/H2O, which are capable of photocatalytic overall water splitting. Of particular importance is that three of them based on 2,4,6-tris(4-methylphenyl)-1,3,5-triazine (TST) can split water into hydrogen and oxygen under visible light. Our results agree with respect to the literature, with three of them having been studied for photocatalytic HER or CO2 reduction. In addition, we further experimentally demonstrate that I-TST presents both HER and OER activity under visible light. Our findings present a route to design practical 2D COFs as metal-free and single-material photocatalysts for overall water splitting under visible light.

2.
Adv Mater ; 32(2): e1904433, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31782554

RESUMO

Metal-free polymer photocatalysts have shown great promise for photocatalytic H2 O2 production via two-electron reduction of molecular O2 . The other half-reaction, which is the two-electron oxidation of water, still remains elusive toward H2 O2 production. However, enabling this water oxidation pathway is critically important to improve the yield and maximize atom utilization efficiency. It is shown that introducing acetylene (CC) or diacetylene (CCCC) moieties into covalent triazine frameworks (CTFs) can remarkably promote photocatalytic H2 O2 production. This enhancement is inherent to the incorporated carbon-carbon triple bonds which are essential in modulating the electronic structures of CTFs and suppressing charge recombinations. Furthermore, the acetylene and diacetylene moieties can significantly reduce the energy associated with OH* formation and thus enable a new two-electron oxidation pathway toward H2 O2 production. The study unveils an important reaction pathway toward photocatalytic H2 O2 production, reflecting that precise control over the chemical structures of polymer photocatalysts is vital to achieve efficient solar-to-chemical energy conversion.

3.
ACS Appl Mater Interfaces ; 11(48): 45301-45309, 2019 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-31710457

RESUMO

Soft electronics with the capability of perceiving surrounding objects and acquiring information without direct touch have become increasingly important for applications in remote safety and healthcare monitoring, artificial prosthetics, and augmented reality. So far, materials that are inherently stretchable and can exhibit distinct touchless sensing capability are still scarce. Here, we report that constructing a three-dimensional (3D) segregated structure in the carboxylated styrene-butadiene latex film using poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) can lead to a highly stretchable polymer composite with high sensitivity toward various touchless stimuli. Consequently, the resultant composite can be directly used for touchless sensing. Control experiments reveal that the unique 3D segregated structure is essential to achieve high-performance touchless sensing. We further show that the composite can be assembled into capacitors to precisely identify surrounding objects via capacitive proximity sensing. Moreover, an intelligent prosthetic hand is fabricated by integrating piezoresistive and capacitive sensing modes together, demonstrating that the newly developed polymer composite holds great potential for practical touchless sensing by simultaneously perceiving the location and the temperature of the target.

4.
Small ; 15(43): e1903643, 2019 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-31478337

RESUMO

Ultrathin 2D conjugated polymer nanosheets are an emerging class of photocatalysts for solar-to-chemical energy conversion. Until now, the majority of ultrathin 2D polymer photocatalysts are produced through exfoliation of layered polymers. Unfortunately, it still remains a great challenge to exfoliate layered polymers into ultrathin nanosheets with high yields. In this work, a liquid-phase protonation-assisted exfoliation is demonstrated to enable remarkably improved exfoliation yields of various 2D N-containing conjugated polymers such as g-C3 N4 , C2 N, and aza-CMP. The exfoliation yields are only 2-15% in pure water whereas they can be substantially improved to 41-56% in 12 m HCl. The exfoliated ultrathin nanosheets possess average thicknesses less than 5 nm and can be easily dispersed in aqueous solutions. More importantly, the exfoliated nanosheets exhibit significantly enhanced photocatalytic activity toward photocatalytic water splitting compared to their bulk counterparts. Further characterizations and computational calculations reveal that protonation of the heterocyclic nitrogen sites in the conjugated polymer frameworks can lead to strong hydrogen bonding between the polymer surfaces and water molecules, resulting in facilitated exfoliation of polymers into the liquid phase. This study unveils an important protocol toward producing ultrathin 2D N-containing conjugated polymer nanosheets for future solar energy conversion.

5.
Nano Lett ; 19(6): 4060-4067, 2019 06 12.
Artigo em Inglês | MEDLINE | ID: mdl-31136712

RESUMO

Both diffusion-limited and perfusion-limited hypoxia are associated with tumor progression, metastasis, and the resistance to therapeutic modalities. A strategy that can efficiently overcome both types of hypoxia to enhance the efficacy of cancer treatment has not been reported yet. Here, it is shown that by using biomimetic ultrathin graphdiyne oxide (GDYO) nanosheets, both types of hypoxia can be simultaneously addressed toward an ideal photodynamic therapy (PDT). The GDYO nanosheets, which are oxidized and exfoliated from graphdiyne (GDY), are able to efficiently catalyze water oxidation to release O2 and generate singlet oxygen (1O2) using near-infrared irradiation. Meanwhile, GDYO nanosheets also exhibit excellent light-to-heat conversion performance with a photothermal conversion efficiency of 60.8%. Thus, after the GDYO nanosheets are coated with iRGD peptide-modified red blood membrane (i-RBM) to achieve tumor targeting, the biomimetic GDYO@i-RBM nanosheets can simultaneously enhance tumor reoxygenation and blood perfusion for PDT. This study provides new insights into utilizing novel water-splitting materials to relieve both diffusion- and perfusion-limited hypoxia for the development of a novel therapeutic platform.


Assuntos
Materiais Biomiméticos/uso terapêutico , Carbono/uso terapêutico , Nanoestruturas/uso terapêutico , Neoplasias/terapia , Óxidos/uso terapêutico , Animais , Materiais Biomiméticos/química , Carbono/química , Linhagem Celular Tumoral , Humanos , Camundongos Endogâmicos BALB C , Nanoestruturas/química , Neoplasias/irrigação sanguínea , Neoplasias/metabolismo , Neoplasias/patologia , Óxidos/química , Oxigênio/metabolismo , Fotoquimioterapia , Hipóxia Tumoral
6.
Adv Mater ; 31(19): e1807716, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-30920701

RESUMO

Converting solar energy into concentrated heat is very appealing for various applications. Polypyrrole (PPy) is known to possess excellent photothermal property with low thermal conductivity, and thus is an ideal candidate for solar-thermal energy conversion. However, solar-thermal materials based on PPy or other conducting polymers still exhibit limited energy conversion efficiency due to the lack of effective light-trapping schemes. Here, it is demonstrated that multilayer PPy nanosheets with spontaneously formed surface structures such as wrinkles and ridges via sequential polymerization on paper substrates can dramatically enhance broadband and wide-angle light absorption across the full solar spectrum, leading to an impressive solar-thermal conversion efficiency of 95.33%. The intriguing solar-thermal properties and structural features of multilayer PPy nanosheets can be used for solar heating and photoactuators. Meanwhile, when used for solar steam generation, the measured efficiency could achieve ≈92% under one sun irradiation. The hierarchically multilayer structure is mechanically flexible and robust, holding great potential for practical solar energy utilization. This study provides a simple and straightforward approach toward engineering light-weight and thermally insulating polymers into efficient solar-thermal materials for emerging solar energy-related applications.

7.
Angew Chem Int Ed Engl ; 57(50): 16447-16451, 2018 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-30350910

RESUMO

Quantum dots (QDs), a class of promising candidates for harvesting visible light, generally exhibit low activity and selectivity towards photocatalytic CO2 reduction. Functionalizing QDs with metal complexes (or metal cations through ligands) is a widely used strategy for improving their catalytic activity; however, the resulting systems still suffer from low selectivity and stability in CO2 reduction. Herein, we report that doping CdS QDs with transition-metal sites can overcome these limitations and provide a system that enables highly selective photocatalytic reactions of CO2 with H2 O (100 % selectivity to CO and CH4 ), with excellent durability over 60 h. Doping Ni sites into the CdS lattice leads to effective trapping of photoexcited electrons at surface catalytic sites and substantial suppression of H2 evolution. The method reported here can be extended to various transition-metal sites, and offers new opportunities for exploring QD-based earth-abundant photocatalysts.

8.
Adv Mater ; 30(48): e1801955, 2018 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-30033628

RESUMO

Converting solar energy into storable and transportable chemical fuels using artificial photosynthetic systems can provide an alternative route to the current unsustainable use of fossil fuels, addressing the worldwide energy crisis and environmental issues. Recently, semiconducting polymers have emerged as a very promising class of photocatalysts for water splitting as their electronic and structural properties can be conveniently controlled and systematically designed at a molecular level. Among the various polymer photocatalysts that are reported so far, 2D polymer nanosheets are particularly interesting and gaining more attention. The 2D planar structure offers unique features such as high surface area, abundant surface active sites, efficient charge separation, and facile formation of heterostructures. The design and synthesis of 2D polymer nanosheets have greatly advanced the research in photocatalytic overall water splitting. Here, recent advances in developing photocatalysts based on 2D polymer nanosheets for photocatalytic overall water splitting are highlighted. Specifically, the existing approaches to tune their electronic structures and surface active sites for photocatalysis are discussed. Future opportunities and challenges for developing 2D polymers for photocatalytic overall water splitting are also included.

9.
Small ; 14(28): e1800994, 2018 07.
Artigo em Inglês | MEDLINE | ID: mdl-29806124

RESUMO

Biodegradable transient devices represent an emerging type of electronics that could play an essential role in medical therapeutic/diagnostic processes, such as wound healing and tissue regeneration. The associated biodegradable power sources, however, remain as a major challenge toward future clinical applications, as the demonstrated electrical stimulation and sensing functions are limited by wired external power or wireless energy harvesters via near-field coupling. Here, materials' strategies and fabrication schemes that enable a high-performance fully biodegradable magnesium-molybdenum trioxide battery as an alternative approach for an in vivo on-board power supply are reported. The battery can deliver a stable high output voltage as well as prolonged lifetime that could satisfy requirements of representative implantable electronics. The battery is fully biodegradable and demonstrates desirable biocompatibility. The battery system provides a promising solution to advanced energy harvesters for self-powered transient bioresorbable implants as well as eco-friendly electronics.


Assuntos
Fontes de Energia Elétrica , Próteses e Implantes , Animais , Linhagem Celular , Eletrodos , Camundongos , Imagem Óptica , Ratos Sprague-Dawley
10.
Acc Chem Res ; 51(9): 2169-2178, 2018 09 18.
Artigo em Inglês | MEDLINE | ID: mdl-29771111

RESUMO

Acoustic cavitation (the growth, oscillation, and rapid collapse of bubbles in a liquid) occurs in all liquids irradiated with sufficient intensity of sound or ultrasound. The collapse of such bubbles creates local heating and provides a unique source of energy for driving chemical reactions. In addition to sonochemical bond scission and formation, cavitation also induces light emission in many liquids. This phenomenon of sonoluminescence (SL) has captured the imagination of many researchers since it was first observed 85 years ago. SL provides a direct probe of cavitation events and has provided most of our understanding of the conditions created inside collapsing bubbles. Spectroscopic analyses of SL from single acoustically levitated bubbles as well as from clouds of bubbles have revealed molecular, atomic, and ionic line and band emission riding atop an underlying continuum arising from radiative plasma processes. Application of spectrometric methods of pyrometry and plasma diagnostics to these spectra has permitted quantitative measurement of the intracavity conditions: relative peak intensities for temperature measurements, peak shifts and broadening for pressures, and peak asymmetries for plasma electron densities. The studies discussed herein have revealed that extraordinary conditions are generated inside the collapsing bubbles in ordinary room-temperature liquids: observable temperatures exceeding 15 000 K (i.e., three times the surface temperature of our sun), pressures of well over 1000 bar (more than the pressure at the bottom of the Mariana Trench), and heating and cooling rates in excess of 1012 K·s-1. Scientists from many disciplines, and even nonscientists, have been and continue to be intrigued by the consequences of dynamic bubbles in liquids. As chemists, we are fascinated by the high energy reactions and processes that occur during acoustic cavitation and by the use of SL as a spectroscopic probe of the events during cavitation. Within the chemical realm of SL and cavitation there are many interesting questions that are now answered but also many that remain to be explored, so we hope that this Account reveals to the reader some of the most fascinating of those curiosities as we explore the chemical history of a bubble. The high energy species produced inside collapsing bubbles also lead to secondary reactions from the high energy species created within the collapsing bubble diffusing into the bulk liquid and expanding the range of sonochemical reactions observed, especially in redox reactions relevant to nanomaterials synthesis. Bubbles near solid surfaces deform upon collapse, which lessens the internal heating within the bubble, as shown by SL studies, but introduces important mechanical consequences in terms of surface damage and increased surface reactivity. Our understanding of the conditions created during cavitation has informed the applications of ultrasound to a wide range of chemical applications, from nanomaterials to synthetically useful organic reactions to biomedical and pharmaceutical uses. Indeed, we echo Michael Faraday's observation concerning a candle flame, "There is not a law under which any part of this universe is governed which does not come into play and is touched upon in these phenomena." ( Faraday , M. The Chemical History of a Candle ; Harper & Brothers : New York , 1861 ).

11.
Nano Lett ; 18(4): 2217-2225, 2018 04 11.
Artigo em Inglês | MEDLINE | ID: mdl-29528661

RESUMO

Extensive efforts have been devoted to synthesizing photothermal agents (PTAs) that are active in the first near-infrared (NIR) region (650-950 nm). However, PTAs for photothermal therapy in the second NIR window (1000-1350 nm) are still rare. Here, it is shown that two-dimensional ultrathin polypyrrole (PPy) nanosheets prepared via a novel space-confined synthesis method could exhibit unique broadband absorption with a large extinction coefficient of 27.8 L g-1 cm-1 at 1064 nm and can be used as an efficient PTA in the second NIR window. This unique optical property is attributed to the formation of bipolaron bands in highly doped PPy nanosheets. The measured prominent photothermal conversion efficiency could achieve 64.6%, surpassing previous PTAs that are active in the second NIR window. Both in vitro and in vivo studies reveal that these ultrathin PPy nanosheets possess good biocompatibility and notable tumor ablation ability in the second NIR window. Our study highlights the potential of ultrathin two-dimensional polymers with unique optical properties in biomedical applications.

12.
Angew Chem Int Ed Engl ; 57(13): 3454-3458, 2018 03 19.
Artigo em Inglês | MEDLINE | ID: mdl-29377491

RESUMO

Inspired by natural photosynthesis, Z-scheme photocatalytic systems are very appealing for achieving efficient overall water splitting. Developing metal-free Z-scheme photocatalysts for overall water splitting, however, still remains challenging. The construction of polymer-based van der Waals heterostructures as metal-free Z-scheme photocatalytic systems for overall water splitting is described using aza-fused microporous polymers (CMP) and C2 N ultrathin nanosheets as O2 - and H2 -evolving catalysts, respectively. Although neither polymer is able to split pure water using visible light, a 2:1 stoichiometric ratio of H2 and O2 was observed when aza-CMP/C2 N heterostructures were used. A solar-to-hydrogen conversion efficiency of 0.23 % was determined, which could be further enhanced to 0.40 % by using graphene as the solid electron mediator to promote the interfacial charge-transfer process. This study highlights the potential of polymer photocatalysts for overall water splitting.

13.
ACS Appl Mater Interfaces ; 9(44): 38499-38506, 2017 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-29039647

RESUMO

It is known that introducing metal nanoparticles (e.g., Fe and Co) into N-doped carbons can enhance the activity of N-doped carbons toward the oxygen reduction reaction (ORR). However, introducing metals into N-doped carbons inevitably causes the formation of multiple active sites. Thus, it is challenging to identify the active sites and unravel mechanisms responsible for enhanced ORR activity. Herein, by developing a new N-heterocyclic carbene (NHC)-Co complex as the nitrogen- and metal-containing precursor, we report the synthesis of N-doped carbon nanosheets embedded with Co nanoparticles as highly active ORR catalysts without direct metal-nitrogen bonding. Electrochemical measurements and X-ray absorption spectroscopy indicate that the carbon-nitrogen sites surrounding Co nanoparticles are responsible for the observed ORR activity and stability. Density functional theory calculations further reveal that Co nanoparticles could facilitate the protonation of O2 and thus promote the ORR activity. These results provide new prospects in the rational design and synthesis of heteroatom-doped carbon materials as non-precious-metal catalysts for various electrochemical reactions.

14.
Sci Adv ; 3(9): e1701222, 2017 09.
Artigo em Inglês | MEDLINE | ID: mdl-28879237

RESUMO

Physically transient electronics, a form of electronics that can physically disappear in a controllable manner, is very promising for emerging applications. Most of the transient processes reported so far only occur in aqueous solutions or biofluids, offering limited control over the triggering and degradation processes. We report novel moisture-triggered physically transient electronics, which exempt the needs of resorption solutions and can completely disappear within well-controlled time frames. The triggered transient process starts with the hydrolysis of the polyanhydride substrate in the presence of trace amounts of moisture in the air, a process that can generate products of corrosive organic acids to digest various inorganic electronic materials and components. Polyanhydride is the only example of polymer that undergoes surface erosion, a distinct feature that enables stable operation of the functional devices over a predefined time frame. Clear advantages of this novel triggered transience mode include that the lifetime of the devices can be precisely controlled by varying the moisture levels and changing the composition of the polymer substrate. The transience time scale can be tuned from days to weeks. Various transient devices, ranging from passive electronics (such as antenna, resistor, and capacitor) to active electronics (such as transistor, diodes, optoelectronics, and memories), and an integrated system as a platform demonstration have been developed to illustrate the concept and verify the feasibility of this design strategy.

15.
Adv Mater ; 29(38)2017 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-28833545

RESUMO

Direct water splitting into H2 and O2 using photocatalysts by harnessing sunlight is very appealing to produce storable chemical fuels. Conjugated polymers, which have tunable molecular structures and optoelectronic properties, are promising alternatives to inorganic semiconductors for water splitting. Unfortunately, conjugated polymers that are able to efficiently split pure water under visible light (400 nm) via a four-electron pathway have not been previously reported. This study demonstrates that 1,3-diyne-linked conjugated microporous polymer nanosheets (CMPNs) prepared by oxidative coupling of terminal alkynes such as 1,3,5-tris-(4-ethynylphenyl)-benzene (TEPB) and 1,3,5-triethynylbenzene (TEB) can act as highly efficient photocatalysts for splitting pure water (pH ≈ 7) into stoichiometric amounts of H2 and O2 under visible light. The apparent quantum efficiencies at 420 nm are 10.3% and 7.6% for CMPNs synthesized from TEPB and TEB, respectively; the measured solar-to-hydrogen conversion efficiency using the full solar spectrum can reach 0.6%, surpassing photosynthetic plants in converting solar energy to biomass (globally average ≈0.10%). First-principles calculations reveal that photocatalytic H2 and O2 evolution reactions are energetically feasible for CMPNs under visible light irradiation. The findings suggest that organic polymers hold great potential for stable and scalable solar-fuel generation.

16.
J Am Chem Soc ; 139(27): 9136-9139, 2017 07 12.
Artigo em Inglês | MEDLINE | ID: mdl-28651432

RESUMO

Creating ordered two-dimensional (2D) metal-organic framework (MOF) nanosheets has attracted extensive interest. However, it still remains a great challenge to synthesize ultrathin 2D MOF nanosheets with controlled thickness in high yields. In this work, we demonstrate a novel intercalation and chemical exfoliation approach to obtain MOF nanosheets from intrinsically layered MOF crystals. This approach involves two steps: first, layered porphyrinic MOF crystals are intercalated with 4,4'-dipyridyl disulfide through coordination bonding with the metal nodes; subsequently, selective cleavage of the disulfide bond induces exfoliation of the intercalated MOF crystals, leading to individual freestanding MOF nanosheets. This chemical exfoliation process can proceed efficiently at room temperature to produce ultrathin (∼1 nm) 2D MOF nanosheets in ∼57% overall yield. The obtained ultrathin nanosheets exhibit efficient and far superior heterogeneous photocatalysis performance compared with the corresponding bulk MOF.

17.
Small ; 13(21)2017 06.
Artigo em Inglês | MEDLINE | ID: mdl-28398009

RESUMO

Developing cost-effective electrocatalysts with high activity and stability for hydrogen evolution reaction (HER) plays an important role in modern hydrogen economy. Amorphous molybdenum sulfide (MoSx ) has recently emerged as one of the most promising alternatives to Pt-based catalysts in HER, especially in acidic electrolytes. Here this study reports a simple ultrasonic spray pyrolysis method to synthesize hybrid HER catalysts composed of MoSx firmly attached on entangled carbon nanotube nanospheres (MoSx /CNTs). This synthetic process is fast, continuous, highly durable, and amenable to high-volume production with high yields and exceptional quality. The MoSx /CNTs hybrid catalyst prepared at 300 °C exhibits a low overpotential of 168 mV at the current density of 10 mA cm-2 with a small Tafel slope of 36 mV dec-1 . Electrochemical measurements and X-ray photoelectron spectroscopy analyses reveal that the CNT network not only promotes the charge transfer in corresponding HER process but also enhances the stability of the active sites in MoSx . This work demonstrates that ultrasonic spray pyrolysis is a reliable and versatile approach for synthesizing amorphous MoSx -based HER catalysts.

18.
ACS Appl Mater Interfaces ; 9(16): 14180-14186, 2017 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-28387517

RESUMO

N-doped carbon materials is of particular attraction for anodes of lithium-ion batteries (LIBs) because of their high surface areas, superior electrical conductivity, and excellent mechanical strength, which can store energy by adsorption/desorption of Li+ at the interfaces between the electrolyte and electrode. By directly carbonization of zeolitic imidazolate framework-8 nanospheres synthesized by an emulsion-based interfacial reaction, we obtained N-doped hollow carbon nanospheres with tunable shell thickness (20 nm to solid sphere) and different N dopant concentrations (3.9 to 21.7 at %). The optimized anode material possessed a shell thickness of 20 nm and contained 16.6 at % N dopants that were predominately pyridinic and pyrrolic. The anode delivered a specific capacity of 2053 mA h g-1 at 100 mA g-1 and 879 mA h g-1 at 5 A g-1 for 1000 cycles, implying a superior cycling stability. The improved electrochemical performance can be ascribed to (1) the Li+ adsorption dominated energy storage mechanism prevents the volume change of the electrode materials, (2) the hollow nanostructure assembled by the nanometer-sized primary particles prevents the agglomeration of the nanoparticles and favors for Li+ diffusion, (3) the optimized N dopant concentration and configuration facilitate the adsorption of Li+; and (4) the graphitic carbon nanostructure ensures a good electrical conductivity.

19.
Chem Soc Rev ; 46(10): 2799-2823, 2017 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-28368055

RESUMO

Heterogeneous catalysts have been widely used for photocatalysis, which is a highly important process for energy conversion, owing to their merits such as easy separation of catalysts from the reaction products and applicability to continuous chemical industry and recyclability. Yet, homogenous photocatalysis receives tremendous attention as it can offer a higher activity and selectivity with atomically dispersed catalytic sites and tunable light absorption. For this reason, there is a major trend to combine the advantages of both homogeneous and heterogeneous photocatalysts, in which coordination chemistry plays a role as the bridge. In this article, we aim to provide the first systematic review to give a clear picture of the recent progress from taking advantage of coordination chemistry. We specifically summarize the role of coordination chemistry as a versatile tool to engineer catalytically active sites, tune light harvesting and maneuver charge kinetics in heterogeneous photocatalysis. We then elaborate on the common fundamentals behind various materials systems, together with key spectroscopic characterization techniques and remaining challenges in this field. The typical applications of coordination chemistry in heterogeneous photocatalysis, including proton reduction, water oxidation, carbon dioxide reduction and organic reactions, are highlighted.

20.
Nanoscale ; 9(12): 4090-4096, 2017 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-28294255

RESUMO

Nanostructured semiconducting polymers have emerged as a very promising class of metal-free photocatalytic materials for solar water splitting. However, they generally exhibit low efficiency and lack the ability to utilize long-wavelength photons in a photocatalytic oxygen evolution reaction (OER). Here, based on first-principles calculations, we reveal that the two-dimensional (2D) aza-fused conjugated microporous polymer (aza-CMP) with a honeycomb network is a semiconductor with novel layer-dependent electronic properties. The bandgap of the as-synthesized aza-CMP nanosheets is measured to be 1.22 eV, suggesting that they can effectively boost light absorption in the visible and near infrared (NIR) region. More importantly, aza-CMP also possesses a valence band margin suitable for a photocatalytic OER. Taking advantage of the 2D layered nanostructure, we further show that the exfoliated ultrathin aza-CMP nanosheets can exhibit a three-fold enhancement in the photocatalytic OER. After deposition of a Co(OH)2 cocatalyst, the hybrid Co(OH)2/aza-CMP photocatalyst exhibits a markedly improved performance for photocatalytic O2 evolution. Furthermore, first-principles calculations reveal that the photocatalytic O2 evolution reaction is energetically feasible for aza-CMP nanosheets under visible light irradiation. Our findings reveal that nanostructured polymers hold great potential for photocatalytic applications with efficient solar energy utilization.

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