摘要
纳米片与空心球上之间的合理界面调控是开发高效太阳能制氢光催化剂的潜在策略。在各类光催化材料中,金属硫化物由于具有相对较窄的带隙和优越的可见光响应能力而被广泛研究。ZnIn_(2)S_(4)是一种层状的三元过渡金属半导体光催化剂,其带隙可控(约2.4 eV)。在众多金属硫化物光催化剂中,ZnIn_(2)S_(4)引起了广泛兴趣。然而,单纯的ZnIn_(2)S_(4)光催化活性仍然相对较差,主要是因为光生载流子的复合率较高、迁移速率较慢。在半导体光催化剂上负载助催化剂是提升光催化剂性能的一种有效方法,因为它不仅可以加速光生电子和空穴的分离,而且还可以降低质子还原反应的活化能。作为一种三元过渡金属硫化物,NiCo_(2)S_(4)表现出较高的导电性、较低的电负性、丰富的氧化还原特性以及优越的电催化活性。这些特性表明,NiCo_(2)S_(4)可以作为光催化制氢的助催化剂,以加速电荷分离和转移。此外,NiCo_(2)S_(4)和ZnIn_(2)S_(4)都属于三元尖晶石的晶体结构,这可能有助于构建具有紧密界面接触的NiCo_(2)S_(4)/ZnIn_(2)S_(4)复合物,从而提高光催化性能。本文中,将超薄ZnIn_(2)S_(4)纳米片原位生长到非贵金属助催化剂NiCo_(2)S_(4)空心球上,形成具有强耦合界面和可见光吸收的NiCo_(2)S_(4)@ZnIn_(2)S_(4)分级空心异质结构光催化剂。最优NiCo_(2)S_(4)@ZnIn_(2)S_(4)复合样品(NiCo_(2)S_(4)含量:ca.3.1%)的析氢速率高达78μmol·h−1,约是纳米片组装ZnIn_(2)S_(4)光催化剂析氢速率的9倍、约是1%(w,质量分数)Pt/ZnIn_(2)S_(4)样品析氢速率的3倍。此外,该复合光催化剂在反应中表现出良好的稳定性。荧光和电化学测试结果表明,NiCo_(2)S_(4)空心球是一种有效的助催化剂,可促进光生载流子的分离和传输,并降低析氢反应的活化能。最后,提出了NiCo_(2)S_(4)@ZnIn_(2)S_(4)光催化析氢的可能反应机理。在NiCo_(2)S_(4)@ZnIn_(2)S_(4)复合
The rational interface tailoring of nanosheets on hollow spheres is a promising strategy to develop efficient photocatalysts for hydrogen production with solar energy.Among the various photocatalyst materials,metal sulfides have been extensively researched because of their relatively narrow band gap and superior visible-light response.ZnIn(2)S_(4) is a layered ternary chalcogenide semiconductor photocatalyst with a tunable band gap energy(approximately 2.4 eV).Among various metal sulfide photocatalysts,ZnIn(2)S_(4) has gained considerable attention.However,intrinsic ZnIn(2)S_(4) only exhibits a relatively moderate photocatalytic activity,which is mainly owing to the high recombination and low migration rate of photocarriers.Loading cocatalysts onto semiconductor photocatalysts is an effective way to improve the performance of photocatalysts,because it can not only facilitate the separation of electron-hole pairs,but also reduce the activation energy for proton reduction.As a ternary transition metal sulfide,NiCo_(2)S_(4) features a high electrical conductivity,low electronegativity,excellent redox properties,and outstanding electrocatalytic activity.Such favorable characteristics suggest that NiCo_(2)S_(4) can expedite charge separation and transfer,thereby promoting photocatalytic H2 production by serving as a cocatalyst.Moreover,both NiCo_(2)S_(4) and ZnIn(2)S_(4) possess the ternary spinel crystal structure,which may facilitate the construction of NiCo_(2)S_(4)/ZnIn(2)S_(4) hybrids with tight interfacial contact for an enhanced photocatalytic performance.Herein,ultrathin ZnIn(2)S_(4) nanosheets were grown in situ on a non-noble-metal cocatalyst,namely NiCo_(2)S_(4) hollow spheres,to form hierarchical NiCo_(2)S_(4)@ZnIn(2)S_(4) hollow heterostructured photocatalysts with an intimately coupled interface and strong visible light absorption extending to ca.583 nm.The optimized NiCo_(2)S_(4)@ZnIn(2)S_(4) hybrid with a NiCo_(2)S_(4) content of ca.3.1%exhibited a high hydrogen evolution rate of 78μmol·h−1,which w
作者
熊壮
侯乙东
员汝胜
丁正新
王伟俊
汪思波
Zhuang Xiong;Yidong Hou;Rusheng Yuan;Zhengxin Ding;Wee-Jun Ong;Sibo Wang(State Key Laboratory of Photocatalysis on Energy and Environment,College of Chemistry,Fuzhou University,Fuzhou 350116,China;School of Energy and Chemical Engineering,Xiamen University Malaysia,Selangor Darul Ehsan 43900,Malaysia;College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,Fujian Province,China)
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
2022年第7期56-65,共10页
Acta Physico-Chimica Sinica
基金
国家重点研发计划(2021YFA1502100)
国家自然科学基金(U1805255)
国民核生化灾害防护国家重点实验室开放基金(SKLNBC2020-18)资助项目。
关键词
光催化
产氢
助催化剂
金属硫化物
Photocatalysis
H2 production
Cocatalyst
Metal sulfides
