JOURNAL OF CATALYSIS
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2022
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IF 8.047
Zhidong Yang,Ya Zhang,Hongxia Zhang,Jianghong Zhao,Hu Shi,Ming Zhang,Hengquan Yang,Zhanfeng Zheng,Pengju Yang
Photocatalytic CO 2 reduction into valuable chemicals and fuels is thought to be an effective way to reduce greenhouse gas emissions and achieve sustainable carbon cycling. Recent studies have confirmed that polymeric carbon nitride (PCN) can drive CO 2 reduction reaction under visible light irradiation. However, the pristine PCN typically suffers from moderate efficiency. Herein, nitrogen-vacancies-functionalized PCN (NV S -PCN) photocatalysts are successfully prepared via a novel formic acid-assisted etching protocol for the first time. It is found that the NVs are mainly stemmed from the selectively breaking of surface N-(C) 3 sites within PCN matrix. Steady-state photoluminescence (PL), time-resolved PL, and photocurrent results approve that the NVs can significantly suppress the recombination of photogenerated charge carriers. CO 2 temperature programmed desorption and DFT calculations determine that the NVs modification can optimize the electronic properties of NVs-PCN photosystem, and thus considerably improve the activation of CO 2 , while lower the formation barrier of COOH* intermediates. Consequently, the NVs-PCN photosystem exhibits a 279-fold improvement in CO 2 reduction activity over the pristine PCN under 400 nm light irradiation. Moreover, we successfully prepare another NVs-modified PCN-T (trithiocyanuric acid as a precursor) under the same preparation conditions. This NVs-PCN-T photosystem also shows exceptional performances for photocatalytic CO 2 reduction and hydrogen production with visible light. The apparent quantum yields (AQYs) for CO 2 reduction and hydrogen production reach as high as 6.17 % and 31.08 % at 400 nm, respectively. The insights provided in this work are expected to provide a novel clue for manipulating catalytic properties and advancing the in-depth understanding on the role of defect structure of photocatalysts during CO 2 reduction.
研究领域:
材料科学
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环境科学
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催化化学
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DOI
高影响因子
Journal of Physical Chemistry Letters
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2023
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IF 5.7
Huiling Tang,Shuang Xu,Mingjie Li,Liqin Wu,Chenghao Duan,Huiming Luo,Biao Zhou,Mumin Rao,Yongcai Qiu,Guangxu Chen,Keyou Yan
Biomass ethanol is regarded as a renewable resource but it is not economically viable to transform it to high-value industrial chemicals at present. Herein, a simple, green, and low-cost CuCl2–ethanol complex is reported for ethanol dehydration to produce ethylene and acetal simultaneously with high selectivity under sunlight irradiation. Under N2 atmosphere, the generation rates of ethylene and acetal were 165 and 3672 μmol g–1 h–1, accounting for 100% in gas products and 97% in liquid products, respectively. An outstanding apparent quantum yield of 13.2% (365 nm) and the maximum conversion rate of 32% were achieved. The dehydration reactions start from the photoexcited CuCl2–ethanol complex, and then go through the energy transfer (EnT) and ligand to metal charge transfer (LMCT) mechanisms to produce ethylene and acetal, respectively. The formation energies of the CuCl2–ethanol complex and the key intermediate radicals (e.g., ·OH, CH3CH2·, and CH3CH2O·) were validated to clarify the mechanisms. Different from previous CuCl2-based oxidation and addition reactions, this work is anticipated to supply new insights into the dehydration reaction of ethanol to produce useful chemical feedstocks.
研究领域:
催化
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绿色化学
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有机转化
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光化学
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生物质转化
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
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IF 21.1
Yong Li,Yuanyuan Wu,Dongting Wang,Xinjia Zhang,Tianyuan Xiao,Jianhua Zheng,Guoqiang Zhang
Non-radiative and radiative recombination jointly determine the photogenerated-carrier separation efficiency of photocatalysts. However, linear conjugated polymer photocatalysts (LCPP) still suffer from serious non-radiative recombination caused by exciton-phonon coupling and radiative recombination originating from exciton radiative transition. Herein, we report a strategy to simultaneously suppress non-radiative and radiative recombination in LCPP, which successfully addresses this drawback. Firstly, we successfully synthesized 2D Poly(4,7-dithienyl-2,1,3-benzothiadiazole) (PDTBT) with N…S intramolecular conformational locks to suppress non-radiative recombination. The obtained PDTBT exhibits largely expanded absorption range and efficiently suppressed exciton–phonon coupling. Subsequently, we constructed 2D/2D PDTBT/graphitic carbon nitride (CN) polymer heterojunctions to suppress radiative recombination, and the obtained 25PDTBT/CN exhibits hydrogen production activity up to 17.09 mmol h −1 g −1 with the apparent quantum yields ( AQYs ) of 13.65 % at 700 nm and 4.36 % at 750 nm. The excellent photocatalytic activities are proved to originate from the effectively suppressed exciton-phonon coupling by N…S intramolecular conformational locks and the efficient photogenerated-carrier transfer via van der Waals forces between PDTBT and CN. This research offers a practical approach for suppressing non-radiative and radiative recombination of linear conjugated polymer and constructing efficient 2D/2D polymer heterojunctions.
研究领域:
材料科学
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化学工程
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纳米技术
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物理化学
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高分子科学
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产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
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2025
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IF 8.2
Hong Qian,Binxia Yuan,Yuhao Liu,Rui Zhu,Chengxi Zhang,Hexing Li
Photocatalytic CO2 reduction to renewable fuels presents a promising strategy to mitigate greenhouse effects, yet challenges persist in achieving high efficiency due to CO2’s thermodynamic stability and competitive H2O adsorption. Herein, we develop a superhydrophobic photochromic TiO2/Bi2Wo6 (TBW-2O) nanocomposite that synergistically enhances visible-light-driven CO2 reduction. Dynamic charge management via reversible W6+↔W5+ transitions not only suppresses charge recombination but also facilitates electron transfer for CO2 activation, as evidenced by in situ XPS and EPR. The superhydrophobic surface designed with sodium oleate (water contact angle >150°) selectively enriches CO2 at the active sites compared to H2O (ΔGCO2 = −2.88 eV vs ΔGH2O = −1.17 eV). Dual heterojunction effects (Type II + Z-scheme) between TiO2 and Bi2WO6 optimize light absorption and redox potentials. The optimized TBW-2O achieves exceptional CH4 and CO production rates of 48.09 and 37.40 μmol·g–1·h–1, respectively, representing 19.7- and 6.6-fold enhancements over pure TiO2. Notably, it attains an apparent quantum yield (AQY) of 0.35% (CH4) and 0.32% (CO) at 350 nm without sacrificial agents or noble metals. Combined experimental and theoretical analyses reveal that the W6+/W5+ redox cycle and hydrophobic interface collaboratively promote COOH/CHO intermediate formation, steering the reaction pathway toward CH4. This work provides a design blueprint for multifunctional photocatalysts integrating photochromism and surface wettability control.
研究领域:
环境科学
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材料科学
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化学工程
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纳米技术
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催化
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物理化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of the American Chemical Society
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2024
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IF 14.4
Fan Ma,Zhi-Mei Luo,Jia-Wei Wang,Gangfeng Ouyang
The development of efficient, selective, and durable CO2 photoreduction systems presents a long-standing challenge in full aqueous solutions owing to the presence of scarce CO2 and the fierce competition against H2 evolution, which is even more challenging when noble metals are not utilized. Herein, we present the facile decorations of four phosphonic acid groups on a donor–acceptor-type organic dye to obtain a water-soluble photosensitizer (4P-DPAIPN), which succeeds the excellent photophysical and photoredox properties of its prototype, exhibiting long-lived delayed fluorescence (>10 μs) in aqueous solutions. Combining 4P-DPAIPN with a cationic cobalt porphyrin catalyst has accomplished record-high apparent quantum yields of 9.4–17.4% at 450 nm for CO2-to-CO photoconversion among the precedented systems (maximum 13%) in fully aqueous solutions. Remarkable selectivity of 82–93% and turnover number of 2700 for CO production can also be achieved with this noble-metal-free system, outperforming a benchmarking ruthenium photosensitizer and a commercial organic dye under parallel conditions. Such high performances of 4P-DPAIPN can be well maintained under real sunlight. More impressively, no significant decomposition of 4P-DPAIPN was detected during the long-term photocatalysis. Eventually, the photoinduced electron transfer pathways were proposed.
研究领域:
化学
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材料科学
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环境科学
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光化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
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